CN1301853C - Colour shifting film - Google Patents

Abstract

Multilayer polymeric films and other optical bodies are provided which are useful in making colored mirrors and polarizers. The films are characterized by a change in color as a function of viewing angle.

Description

Colour shifting film

Scope of the present invention

The present invention relates generally to blooming, but relate to the blooming that changes color with the visual angle more precisely.

Background of invention

The invention belongs to useful blooming aspect the colour demonstration.This demonstration be often as making the data of being showed cause a kind of method that people gaze at, or in displaying and when selling a certain specific object aroused attention.These are showed and usually to be used on signal light (for example, outdoor advertising case and road signal light), telephone booth and the packaging material various in style.

If it is make that of it the color of demonstration is become with the visual angle, then just more favourable.This being commonly referred to as " color transition demonstration " is even also be significant and be used for guiding spectators to putting on display the attention of object in the periphery observation.

In the past, usually print on the paperboard or the transparent printing ink that gets on translucent substrate is delivered to color and shows that thing gets on by absorption.But these printing ink all can not change color usually.(in other words, these color of ink generally can not change with the visual angle).

Also develop some color shifting inks, be mainly used in Secure Application.Yet except their sizable expense, the printing ink of some this pattern generally is lighttight, so be not suitable in the application of illuminating at the back side.And these printing ink are normally piled layer according to the multilayer of isotropic material, thereby will lose colour saturation when the visual angle increases.

Camouflage paint is also known.For example, gang's light interfere pigment can be from Flex Products, and Inc. buys under trade sign CHROMAFLAIR, and these pigment have been used to make decalcomania.The product document is described as these decalcomanias to be made of camouflage paint in the commercial pigments prescription, so, be used on the vinyl substrate.Yet the discoloration effect that is provided by these materials only just can be observed at place, sizable oblique angle, and is only limited to the transformation between two kinds of colors.Also have, at United States Patent (USP) the 5th, 084, No. 351 people such as () Phillips, United States Patent (USP) the 5th, 569, No. 535 (people such as Phillips) and United States Patent (USP) 5,570, No. 847 (people such as Phillips) (these materials have all transferred Flex Products, Inc.) narration of being understood.These materials all present quite low intensity of colour (for example referring to United States Patent (USP) the 5th, 084, Fig. 7 of No. 351-9).Materials similar is also at United States Patent (USP) the 5th, 437, narration in No. 931 people such as () Tsai.

A kind of plastic foil of flash of light is just sold by EngelhardCorporation under trade mark Blackm Magic at present.This film is once at " cosmetics and personal health magazine " (the Cosmetic ﹠amp in 9-10 month in 1997; Personal CareMagazine) go up with thick 17.8 microns (0.7 Mills) semi-transparent film that tinges black above 100 layers, do advertisement, it can provide and be similar to neontetrafish, peacock feather and the oil film effect of seeing.This plastic foil is the multilayer heap layer of blooming.In varied in thickness cause change color in whole film district.Though the deviation of bed thickness and its mean value is little it to change color in the adjacent side zone be significant.The various types of film is not marked as single reflection colour and replaces and be marked as double-deck color film.For example, its medium blue/green and red/green combined colors can be buied on market.

Also developed other variable color film.Wherein some film is the multilayer film based on metal, slaine or other inorganic material.Therefore, United States Patent (USP) the 4th, 735, No. 869 (Morita) narrated the titanium dioxide multilayer film, and it demonstrates the various combinations (for example: have the green reflection of magenta transmission) of reflection and transmitted colors.

Other multi-layer colour-changing film is known to be polymer.Therefore, United States Patent (USP) the 5th, 122,095 people such as () Wheatley notice that by the color of these film reflections and the angle of the incident light that shines this film be relevant in the film of narration United States Patent (USP) the 3rd, 711,176 (Alfery, people such as Jr.).But because the color transition of seeing on these films is very mild, colour saturation is also very poor, more very, shows so these films are not suitable for colour when acute angle.Therefore need a kind of variable color film useful in display application in this area, as function of viewing angle, it can demonstrate distinct variable color and keep also needing uniformly coloured polymer to interfere filter in high colour saturation this area.

Utilize strain hardening (for example semi-crystal or crystal) material, produced various birefringence optical films.Because these materials desired coupling and mismatch aspect refractive index can be good so these materials have been proved in the production of multi-layer optical film by regulating the orientation acquisition.This film was narrated, for example, and in WO 96/19347.

WO 97/01726 relates to a kind of back of the body irradiation system, and it comprises: the photoconduction (lightguide) that limits the back side; Be connected to the light source of photoconduction with optical mode, wherein, light source is launched light into photoconduction; And the back of the body emitter at the close photoconduction back side.Back reflector comprises multi-layer optical film, and the light of 60 ° of angle incidents of normal is left on the edge that it reflects about 80% normal incident light and at least 80% at least.

EP-A-0491551 relates to a kind of condensate of height reflection of multilayer, and it comprises at least two types optical layers, and this condensate is a thermoformable, and can make film, sheet and various parts, but still keeps uniform reflection appearance.The condensate of reflection comprises first and second different types of polymeric materials at least, and first and second polymeric materials have abundant layer, thereby are reflected with 30 ° of light that are incident on this condensate at least.The optical thickness of some layer is between 0.09 to 0.45 micron, and the optical thickness of remainder layer is not more than 0.09 micron or be not less than 0.45 micron.The refractive index of first and second polymeric materials is unequal mutually, differs from 0.03 at least.Can do synusia, rustless metal outward appearance article and parts, reflector and mirror lens to reflector.

Also need polymer multi-layer blooming with good colour uniformity in this area.Be found in the distortion height sensitivity aspect thickness and the optical layer thickness with the multilayer film of the polymeric material manufacturing of extruding, it causes change in color and impure on the transmembrane width.This problem was commented on (R.van Renesse compiles, 1994) at " optics file security " (Optical Document Security) 251-252.In the multi-layer polymer film that narration is produced up till now by Dow Chemical Company and their licensee Mearl Corporation, document points out that control other varied in thickness is very difficult in these films, the result, film demonstrates " countless versicolor narrow colo(u)r streaks seldom is wider than the 2-3 millimeter " (the same 251.) also at the 5th, 217, No. 794 (Schrenk) the 11st row of the patent United States Patent (USP) of Dow, 19-32 is capable to be proposed this problem, being used to of pointing out there to narrate therein the technology of making film can cause 300% or more bed thickness change.At the 10th row, 17-28 is capable, and document points out that it is the characteristic with multilayer polymeric object of optics thin layer (in other words, optical thickness is less than about 0.7 micron thin layer).It demonstrates colo(u)r streak heterogeneous and color spot.About United States Patent (USP) the 3rd, 711, also in the 2nd row, 18-21 is capable to have ever made the same evaluation of the film of No. 176 (Alfrey, people such as Jr.).Owing to the explanation of these documents, need have the polymer multi-layer blooming (and the method for making it) of high color homogeneity in the art for a long time.

Known other polymer multi-layer bloomings, their the main zone of reflections depend on the optics extremely thin thin layer on the thick or optics.This film has been avoided some halation problem of running at other multi-layer polymer films, mainly is because the halation band all leans on to such an extent that too near so that human eyes can't be differentiated.But, because being higher hamonic wave by the principal reflection band of the region of ultra-red that is positioned at spectrum, visible reflection of light provided, be to be compromised so film produces the ability of the high reflectance of visible light.Also need multiple layer polymer blooming (with a method of making same film) in this area, its principal reflection band by on the optics thin (for example, have at 0.01 micron to 0.45 micron optical thickness) generation, and demonstrate the color of high uniformity, these and other needs colour shifting film of the present invention to satisfy, as what described hereinafter.

Summary of the invention

In one aspect, the invention belongs to plurality of layers of double refraction variable color film and other optical bodies they to the axle (x-axle and y-axle) of mutually orthogonal in the plane and along the polarised light of spool (the z-axle) of the axle in the vertical plane in succession refractive index between have special relation.Especially, along x-, y-, with the difference (be respectively Δ x, Δ y and Δ z) of z-axle on refractive index be such, thereby the absolute value of Δ z less than bigger one pact of the absolute value of the absolute value of Δ x and Δ y half (for example, | Δ z|＜0.5k, k=max{| Δ x |, | Δ y|}).Can make have this character film to present transmitted spectrum, wherein, for the p-polarised light, the width of transmission or reflection peak and intensity (when the function as frequency, or 1/ λ when mapping) remain unchanged in one of the visual angle very big scope substantially.Also have,, compare its spectrum with the spectral characteristic of isotropism membrane stack layer for shift to the blue region of spectrum with higher rate for the p-polarised light.

On the other hand, the invention belongs to variable color film with at least one zone of reflections.Under the suitable selection of the numerical chracter of birefringence, z-refractive index mismatch, and the f-ratio value of heap layer, to the zone of reflections of s-and p-polarised light or short wavelength band edge or long wavelength's belt edge, under all incidence angles, all roughly meet.When adopting belt edge sharpening (sharpening) art designs of describing in this article, the film of this pattern presents for being used for the long-pending presumable maximum excitation of membrane stack that wide-angle and wave-length coverage design.Except that rapid color transition and high excitation, these films are good in the application of the unpolarized color splitter of needs.

In yet another aspect, the invention belongs to the colour shifting film that has an optical stack layer at least, wherein, the optical thickness of tunic out of the ordinary partly (for example changes along a direction monotonously at first of heap layer, increase or reduce), then, change monotonously or remain unchanged along a different direction at the second portion of heap layer at least.Colour shifting film with heap layer design of this pattern presents steep belt edge on the one side or the both sides of the zone of reflections, and a feasible function film as the visual angle presents rapid change color.Be good in the application of the film that obtains aspect hope has the displaying of rapid noticeable color transition.

Aspect also having one, the invention belongs to a kind of like this film, its main peak in transmitted spectrum is separated out by high delustring, even and when sinking in the high refractive index medium, all exist under all incidence angles for the high delustring band of p-polarised light.The film that obtains all presents the colour saturation of height under all incidence angles.

Also having aspect another, the invention belongs to a kind ofly, but, do not reflecting the film of the visible light of remarkable quantity vertically fashionable with high efficiency reflection near-infrared radiation.This film can comprise that the 1/4 ripple heap layer of two kinds of material compositions can comprise that maybe three kinds or more kinds of material make an optical stack layer, it can suppress one or more higher hamonic waves of principal reflection band or a plurality of zones of reflections, this also can comprise polymeric layer A, B and C by utilization, and reach, and realize between the refraction coefficient of these materials that certain concerns and obtain by the tactic optical repeat unit of ABC.By specifying n _x ^aAnd n _y ^aBe respectively along the refractive index of the polymeric layer A of x axle in the plane and y axle, n _x ^bAnd n _y ^bBe respectively along the refractive index of the polymeric layer B of x axle in the plane and y axle, n _x ^cAnd n _y ^cBe respectively along the refractive index of the polymeric layer C of x axle in the plane and y axle, and n _z ^a, n _z ^b, and n _z ^cBe respectively the edge and be appreciated that this relation perpendicular to polymeric layer A, the B of the transverse axis z of the axle in the plane and the refractive index of C.So by requiring n _x ^bAt n _x ^aAnd n _x ^cCentre, and n _x ^aGreater than n _x ^c(for example, $n_x^a>n_x^b>n_x^c$ ) and/or require n _y ^bAt n _y ^aAnd n _y ^cCentre, and n _y ^aGreater than n _y ^c(for example, $n_y^a{>n}_y^b>n_y^c$ ), and require two difference n _z ^a-n _z ^bAnd n _z ^b-n _z ^cIn have one at least less than 0, or require described two differences for example in fact all to equal 0[(, $\max \{(n_z^a-n_z^b),(n_z^b-n_z^c)\}<=0$ )] obtain this special relationship.Except that top membrane stack layer structure, the sharpening technique of belt edge is applicable to and produces the rapid transformation that a height from visible light is transmitted to the high delustring of near infrared light.

Aspect also having one, the invention belongs to 2 in the multilayered color-forming shifting film of doing by the stress hardening material, it demonstrates the look uniformity of height at a given incidence angle place, and belong to the method for making this film, wherein, having several principal reflection bands in film at least is to be produced by the optical stack layer in the film with optic thin layer (optical thickness layer in 0.01 to 0.45 micron scope in other words).The uniformity of physics and thickness optics in the optical stack layer with height.The method according to this invention, the non-stress hardening film of prior art run into thickness and the distortion aspect the thickness of optics, avoid by to 2 * 2 to 6 * 6 times of biaxial stretch-formed cast blanks (web) (and more desirable be about 4 * 4 times).It trends towards causing the variation of transverse gage, so change color, it is much smaller to suddenly change.And, can and this allows to be distributed with in the mould layer thicknesses of extruding the possibility of less distortion than the narrower mould of casting film of making same width with one when making stretched film, this is because the thawing of the minute quantity cloth that scatters occurs in narrower mould.Can be by the additional control that utilizes one to have the accurate cast wheel drive machinery acquisition of constant rotational speed for tunic thickness and optical thickness.So design and operation cast are taken turns.Thereby it is vibrationless, otherwise can cause the sotck thinkness change, so in the variation of blank direction generation thickness in succession down.Having been found that does not have these control, and the normal vibration that runs in extrusion is enough to influence significantly the look uniformity, and part is because the low hot strength when the molten state of the stress hardening material that is used to make blooming of the present invention.As a result, the present invention has allowed the product with the polymeric material colour shifting film first, (for example has height look uniformity under its specific visual angle, such film, wherein, under a specific incidence angle, the wavelength value of belt edge transmission or the spectrum of reflected light band is at 10cm at least ²Area on variation be less than 2% approximately.The film of being produced by this method mainly demonstrates homogeneous thickness and optical thickness in the optical stack layer, therefore, causing comparing with the inhomogeneity film of optical thickness with having lower physics, is comparatively sharply and comparatively fast as the color transition of function of viewing angle.

One relevant aspect, the invention belongs to the colour shifting film of making of stress hardening material (for example, stress hardening polyester).The reflection of the zone of reflections or delustring as be tuned to the right refractive index difference of the number of plies of that wavelength band and layer a function and increase.Use shows the stress hardening material of high index of refraction after stretching, produced big refractive index difference when matching with the low refractive index polymer that goes out.Direct ratio ground reduces the required number of plies with other increase of refringence, in addition, the uniformity of bed thickness improves along with the minimizing of the number of plies, because the less number of plies has alleviated dependence to layer multiplier and big feeding device size to produce the required number of plies, so polymer membrane stack layer can be used the precision of bed thickness controlled and make to improve its spectral signature.

Aspect also having one, the present invention relates on the one or more zone of spectrum, play the colour shifting film of poor polarizer effect.These films are in the irreflexive substrate that is laminated to (or cover a with) white, after (such as paperboard blank cardstock), see or see at reflex time to demonstrate color transition when in transmission.The color transition polarizer also can get up to produce various interesting optical effects with other polarizer or combinations of mirrors.

Colour shifting film of the present invention can advantageously be used as the low absorptivity material in demonstration, it provides the bright Show Color with high-luminous-efficiency.By so wideband light source and blooming being coupled together, thereby, can see the shades of colour of light source in transmission or reflection.Just can easily obtain the color that shows.In certain embodiments, film also can get up with the broadband combinations of mirrors.Therefore, for example, when film so with a broadband combinations of mirrors, thereby film is approximate parallel with mirror, but the one section little distance that is separated from each other just can obtain to present the object of 3-D " degree of depth ".Film can be made into multiple different geometry with combined with the high spectrum reflection rate of advantageously utilizing film and the selectivity of angle with different light sources.

The accompanying drawing summary

Fig. 1 is depicted as and shows that rapid spectrum changes and the amplification of the multilayer film of the simplification of design and exaggerative sectional view.

The curve map of the optical thickness of the optical repeat unit that Fig. 2 is made up of the film among Fig. 1 (ORUs).

Fig. 3 is a curve map of being with the physical thickness of the respective layer of leading to multilayer film.

Fig. 4 be Fig. 3 calculating at the axle transmitted spectrum.

Fig. 5 is the curve map of physical thickness with respective layer of the logical multilayer film of band that rapider spectrum changes.

Fig. 6 be Fig. 5 film calculate at the axle transmitted spectrum.

Fig. 7 is the curve map of physical thickness with respective layer of the logical multilayer film of band that more rapid spectrum changes.

Fig. 8 and 9 illustrate respectively Fig. 7 film at axle with from the transmitted spectrum of axle.

Figure 10,12,14 and 16 is curve maps of physical thickness of each other layer of the multilayer film that adds, and

Figure 11,13,15 and 17 illustrate that related film calculates in the axle reflectance spectrum.

Figure 18 is that explanation is to film of the present invention transmitted spectrum about the optics behavior of p-polarised light when vertical incidence and 60 is spent.

Figure 19 is that explanation is to film of the present invention transmitted spectrum about the optics behavior of p-polarised light when vertical incidence and 60 is spent.

Figure 20 is that explanation is spent the transmitted spectrum that the time scholarship and moral conduct is for computer simulation film of the present invention in vertical incidence and 60.

Figure 21 is that explanation is spent the transmitted spectrum that the time scholarship and moral conduct is for computer simulation film of the present invention in vertical incidence and 60.

Figure 22 is the curve map of explanation as the behavior of the relative index of refraction difference of the function of f-ratio value.

Figure 23 is the curve map of explanation as the behavior of the relative peak heights of the function of f-ratio value.

Figure 24 is the chromatic diagram that utilize CIEx-y saturation coordinate of explanation for PEN/PMMA (polymethyl methacrylate) multilayer heap layer.

Figure 25 is the chromatic diagram in the La*b* colour space for PEN/PMMA multilayer heap layer.

Figure 26 is that explanation is to film of the present invention transmitted spectrum about the optics behavior of s-and p-polarised light when vertical incidence and 60 is spent.

Figure 27 is explanation for PEN/PMMA1/4 ripple heap layer is the curve map that 0.5 o'clock the belt edge as the function of incidence angle (in air) changes in f-ratio value.

Figure 28 is explanation for isotropism 1/4 ripple heap layer is the curve map that 0.50 o'clock the belt edge as the function of incidence angle changes in f-ratio value.

Figure 29 is explanation for PEN/PMMA1/4 wavelength heap layer is the curve map that 0.75 o'clock the belt edge as the function of incidence angle (in air) changes in f-ratio value.

Figure 30 is explanation for PEN/PMMA1/4 wavelength heap layer is the curve map that 0.25 o'clock the belt edge as the function of incidence angle (in air) changes in f-ratio value.

Figure 31 is explanation for the curve map as the belt edge variation of the function of incidence angle (in air) of the 1/4 ripple heap layer that is made of PET (PET) and isotropic material.

Figure 32 takes from along the transmitted spectrum that crosses blank direction difference the prior art film.

Figure 33 takes from along blank toward the transmitted light spectrogram that crosses blank direction difference the prior art film.

Figure 34 is a transmitted spectrum of the green pass filter of invention being taken from the different point of the bar direction of growing crosswise.

Figure 35 takes from along the blank transmitted spectrum of the difference of direction down by filter green of the present invention.

Figure 36 takes from along the blank transmitted spectrum of the difference of direction down by colour filter blueness of the present invention.

Figure 37 is the transmitted spectrum that the prior art film is taken from the difference that crosses the blank direction.

Figure 38 is the transmitted spectrum when blueness of the present invention is taken from vertical incidence and 60 and spent s and p-polarised light by filter.

Figure 39 is the transmitted spectrum when green of the present invention is taken from vertical incidence and 60 and spent by filter.

Figure 40 is a transparent transmitted spectrum when cyan (clear_to_cyan) polarizer is taken from vertical incidence and 60 and spent of the present invention.

The transmitted spectrum that Figure 41 is a cyan of the present invention when blue polarizer is taken from vertical incidence and 60 and spent.

Figure 42 is a dark red transmitted spectrum when yellow polarizer is taken from vertical incidence and 60 and spent of the present invention.

Figure 43 is PET/Ecdel of the present invention (Ecdel is the polyether ester that derives from an Eastman Chemicals company) film to the transmitted spectrum of the polarised light that is parallel to stretching and direction that do not stretch.

Figure 44 is a PET/Ecdel film of the present invention to the transmitted light spectrogram of the polarised light that is parallel to stretching and direction that do not stretch.

Figure 45 is the schematic diagram that the optics behavior when colour shifting film of the present invention is at the bottom of it is stacked to diffuse scattering is described.

Figure 46 is the schematic diagram of the optics behavior of explanation colour shifting film of the present invention when it is stacked to black surface.

Figure 47 is the schematic diagram of the optics behavior of explanation colour shifting film of the present invention when it is stacked to the minute surface substrate.

Figure 48 is the schematic diagram of the combined optics behavior of the color transition polarizer of an explanation polarizer of disperse and a minute surface and an optional absorbed layer.

Figure 49 is the logical device of blue filter of the present invention, at detector and the intermembranous transmitted light spectrogram of putting and do not putting paper.

Figure 50 is a peony of the present invention by filter at detector and intermembranous transmitted spectrum when having or not paper.

Figure 51 is a yellow of the present invention by the transmitted spectrum of filter when detector and film have or not paper.

Figure 52 is the curve map as the relative performance index response of the function of wavelength.

Figure 53 is the general assembly principle sketch of explanation Cold Mirrors reflector/infrared transmission device gardening.

Figure 54 is the schematic diagram of explanation Cold Mirrors specular reflector/infrared diffuse device gardening assembly.

Figure 55 is the schematic diagram of explanation peony reflector (amplitude transformer) gardening assembly.

Figure 56 is the schematic diagram of explanation green reflector (shade) gardening assembly.

Figure 57 is that explanation is to the transmitted spectrum of gardening film of the present invention when vertical incidence and 60 is spent.

Figure 58 is taking from along the transmitted spectrum that crosses several points of blank direction of the narrow passband polarizer safety diaphragm made according to the present invention.

Figure 59 is taking from along the transmitted spectrum that crosses several points of blank direction of the narrow passband polarizer safety diaphragm made according to the present invention.

Figure 60 is the calculating transmitted spectrum of making according to the present invention that comprises three groups 50 layers PET/co-PEN safety diaphragm.

Figure 61 is the calculating transmitted spectrum of the PET/co-PEN safety diaphragm that comprises two groups 50 layers and a group 20 layers made according to the present invention.

Figure 62 is the calculating transmitted spectrum of the influence of the different bed thickness in the film that is illustrated among Figure 17-3.

Figure 63 has the transmitted spectrum (spectrum bar code) that f-ratio value is 0.18 multilayer film.

Figure 64 is that a width of cloth has the transmitted spectrum (spectrum bar code) that f-ratio value is 0.33 multilayer film.

Figure 65 is that a width of cloth has the transmitted spectrum (spectrum bar code) that f-ratio value is 0.5 multilayer film.

Figure 66 is a width of cloth Figure 63,64 and 65 build-up curve figure.

Detailed description of the present invention

A. foreword

Colour shifting film of the present invention is optically anisotropic multi-layer polymer film, and they change color as a function at visual angle.Can design these films and at least one bandwidth, reflect one or two polarisation of light, make at least, provide the colour saturation of height thus at acute angle the demonstrating on one side or the steep belt edge in both sides an of reflection bandwidth.

Being controlled at the bed thickness of optical stack layer in the colour shifting film of the present invention and refractive index then is transparent with the polarization (a specific incidence angle) of catoptrical at least one specific wavelength to other wavelength.By handling these bed thickness modestly and along the refractive index of different film axis, film of the present invention can be formed in the effect that has level crossing or polarizer on the one or more SPECTRAL REGIONs.So two kinds of polarisations that film of the present invention can be transferred to the infrared region that can be reflected in spectrum shake, then be transparent in the other parts of spectrum, they are desirable being used for low-E type master window design (fenestration) thus.

Except their high reflectance, film of the present invention also has two characteristics, and this makes them show it is desirable for the colour of some pattern.At first, along with the selection of special material, the form of the light transmission/reflectance spectrum of multilayer film (for example, bandwidth and reflectance value) can be done to such an extent that remain unchanged substantially in the very big scope of incidence angle for the p-polarised light.Because this characteristic has, wine-colored transmission will appear at a broadband mirror film of the narrow transmission band of having of 650nm place during in vertical incidence for example, along with the raising in succession of incidence angle, occur red, yellow, green and blue then.This behavior is with to move a branch of dispersed light beam by a slit in spectroscope similar.In fact, film of the present invention can be used for making a simple spectrophotometer.Secondly, color with the transformation of angle general big than common isotropism multilayer film.

When incidence angle changed, the zone of reflections that forms different shape was striding across the mobile main foundation that is the change color of film as function of viewing angle of spectrum, and can be advantageously used in the initiative many interesting article and the effects of narration below.Many combinations with color reflection transmission are possible.The particulars of various spectrum designs provide as follows.

B. optical stack layer design

B1. the particulars of spectrum design

Generally, colour shifting film of the present invention can design to such an extent that have reflection spectrum characteristic miscellaneous, produces the optical effect that has nothing in common with each other.For example, the belt edge sharpening can be used for making color with angle more noticeable variation to be arranged, or this feature can combine with the light source with or more narrow emission band.Change a kind of way, can obtain by the slope that increases belt edge, or with not reflecting comparably along the softer change color of film of the light of a kind of given polarization state of the membrane plane of quadrature.For example, be exactly this situation with asymmetric biaxial stretch-formed film.This film has more weak reflectivity for the E field along the light of bigger tensile axis along the light ratio of less tensile axis for E field (electromagnetic field).In such film, transmitted light and catoptrical excitation all can be reduced.

If have the material layer of refractive index in the high plane, one thickness axis (Z axle) refractive index is arranged, it equals the Z-axle refractive index of low-index material, if and dispersion of refractive index can be ignored, then when mapping in the frequency space, that is to say that when the function as the wavelength inverse drew figure, the form of transmitted spectrum will not change with angle for the p-polarised light.This effect be incident on from the p-polarised light interface between the single axial birefringence material the Fresnel reflectance factor functional form and derive for the functional form of the f-ratio value of 1/4 ripple of birefringent film heap layer.Suppose that optical axis x, y and z are orthogonal, x and y are in the plane of membrane stack layer, and z is orthogonal to membrane plane.For the birefringent polymer film, x and y are generally to be the quadrature draw direction of film, and the z axle then is perpendicular to the plane of film.Fresnel coefficient for s-polarization and p-polarised light is provided by equation B1-1 and B1-2:

$r_{\mathrm{pp}}=\frac{n_{{2z}^{*}}{n}_{20}\sqrt{n_{1z}^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="Sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">Sin</figure-callout>}}^2{\mathrm{\&theta;}}_0}-n_{{1z}^{*}}{n}_{10}\sqrt{n_{2z}^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="Sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">Sin</figure-callout>}}^2{\mathrm{\&theta;}}_0}}{n_{{2z}^{*}}{n}_{20}\sqrt{n_{1z}^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="Sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">Sin</figure-callout>}}^2{\mathrm{\&theta;}}_0}+n_{{1z}^{*}}{n}_{10}\sqrt{n_{2z}^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2\mathrm{Sin}{\mathrm{\&theta;}}_0}}$ Equation B1-1

$r_{\mathrm{ss}}=\frac{\sqrt{{\mathrm{<figure-callout\; id="10"\; label="n"\; filenames="C9980395501191.png,C9980395501192.png"\; state="\{\{state\}\}">n</figure-callout>}}_{10}^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="Sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">Sin</figure-callout>}}^2{\mathrm{\&theta;}}_0}-\sqrt{{\mathrm{<figure-callout\; id="20"\; label="n"\; filenames="C9980395501072.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_{20}^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="Sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">Sin</figure-callout>}}^2{\mathrm{\&theta;}}_0}}{\sqrt{{\mathrm{<figure-callout\; id="10"\; label="n"\; filenames="C9980395501191.png,C9980395501192.png"\; state="\{\{state\}\}">n</figure-callout>}}_{10}^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="Sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">Sin</figure-callout>}}^2{\mathrm{\&theta;}}_0}+\sqrt{{\mathrm{<figure-callout\; id="20"\; label="n"\; filenames="C9980395501072.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_{20}^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="Sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">Sin</figure-callout>}}^2{\mathrm{\&theta;}}_0}}$ Equation B1-2

N herein ₁₀And n ₂₀Be respectively material 1 and 2 refractive index planar, and n ₁₂And n ₂₂Be along their refractive index ratio θ separately perpendicular to the membrane plane direction ₀Be to be n in refractive index ₀The incidence angle of surrounding medium k.For the equation of rss be identical for isotropic material.

To along the stretching of the quadrature of the monadic stretching membrane that is used for making twin shaft birefringence reflective polarizer and tensile axis not, equation B1-1 and B1-2 also are effective.To the film of the optical axis in membrane plane (wherein these are non-orthogonal or inconsistent with the film draw direction), equation B1-1 also is effective.The performance at the place, azimuth between these need have more deep and broad mathematical description, but required mathematical modeling technique is known in prior art is.

A kind of useful especially optical stack layer is arranged, compare with refractive index difference planar, its two Z-refractive indexes are to equate or near equating.As mentioned above, if in equation B1-1, make n _1zEqual n _2z, so, people can obtain a noticeable result, are exactly r _PpIrrelevant with incidence angle:

$r_{\mathrm{pp}}=\frac{n_{20}-n_{10}}{{\mathrm{<figure-callout\; id="20"\; label="n"\; filenames="C9980395501072.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_{20}+{\mathrm{<figure-callout\; id="10"\; label="n"\; filenames="C9980395501191.png,C9980395501192.png"\; state="\{\{state\}\}">n</figure-callout>}}_{10}}$ Equation B1-3

Top Fresnel reflectance factor r equation and bed thickness are irrelevant, and only indicate interfacial effect.In the membrane stack layer, the accessible reflection size of multilayer membrane stack layer is relevant with all bed thickness widely with bandwidth, because the optical thickness of layer has been determined the phase place that constructive interference is required.Typically, for maximum luminous power, use the heap layer of two elements 1/4 ripple, it has identical optical thickness for every layer in half-wave element.This design allegedly has 0.5 f-ratio value, wherein

F=n ₁d ₁/ (n ₁d ₁+ n ₂d ₂) equation B1-4

N herein ₁And n ₂Be refractive index, d ₁And d ₂Be two-layer physical thickness, and hypothesis is a vertical incidence.To film optical stack layer, 0.5 f-ratio value provides maximum bandwidth and reflectivity.If the heap layer f-ratio value when vertical incidence is designed to 0.5, when first kind of material of hypothesis has higher refractive index then to isotropic material during at rake angle f-ratio value will increase.Can increase, reduce or remain unchanged for the function f-ratio value of birefringent material as incidence angle, this depends on the relation of the z-refractive index of two material components to refractive index in the plane.Calculate the f-ratio value of birefringent material, can calculate the effective phase place or the body index (bulkindex) of every kind of material for the p-polarised light with equation B1-5 in any incidence angle.

$n_{\mathrm{phz}}^{p-\mathrm{pol}}=\frac{n_0}{n_z}{(n_z^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">sin</figure-callout>}}^2{\mathrm{\&theta;}}_0)}^{\frac{1}{2}}$ Equation B1-5

Can calculate with equation B1-6 the s-polarised light

$n_{\mathrm{phz}}^{s-\mathrm{pol}}={({\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2-{\mathrm{<figure-callout\; id="0"\; label="n"\; filenames="C9980395501081.png,C9980395501101.png"\; state="\{\{state\}\}">n</figure-callout>}}_0^2{\mathrm{<figure-callout\; id="2"\; label="sin"\; filenames="C9980395501062.png"\; state="\{\{state\}\}">sin</figure-callout>}}^2{\mathrm{\&theta;}}_0)}^{\frac{1}{2}}$ Equation B1-6

The optical thickness of every kind of material can multiply by the effective phase index that is provided by equation B1-5 and B1-6 with its physical thickness.As long as suitable effective phase place thickness exponential quantity being inserted into the formula of above-mentioned f-ratio value just can obtain the f-ratio value of every kind of polarization under any incidence angle.Can prove, if the Z-refractive index of material mate, so the f-ratio value under all incidence angles can be simply by

F=n ₁₀d ₁/ (n ₁₀d ₁+ n ₂₀d ₂) equation B1-7 provides, it is irrelevant with incidence angle.Therefore the multilayer interference filter of making of the alternating layer of the material that satisfies the z-index of refraction relationship that matches presents and the irrelevant spectral signature (such as reflectivity and part bandwidth) of incidence angle for the p-polarised light.Here in many colour switching demonstration work of Miao Shuing, be important effect for the p-polarised light as the constant spectrum form of the function of angle, and can be used to produce coloured multi-coated interference film that they all have high excitation under all incidence angles.Be illustrated in Figure 18 as one of the multilayer film that the p-polarised light is demonstrated constant reflectance spectrum.

Example B1-1

Film is to make according to routine E1-2, but its casting wheel speed slow approximately 30%.The p-polarised light is shown in Figure 18 in vertical incidence and the transmitted spectrum when 60 spend.The s-polarised light is shown in Figure 19 in vertical incidence and the transmitted spectrum when 60 spend.

Utilize the definition to belt edge and slope given below, this example measured following each value, when vertical incidence the close 600nm place of stopband the bandwidth (543 to 646nm) of a 103nm is arranged and in this stopband average transmittance be 5.5%.The slope at blue zone edge is 0.66% every nm, and the slope on red limit is 2.1% every nm.Bandwidth at the passband at 700nm place when vertical incidence is that 100nm and maximum transmission rate are 85%.Usually, the slope of passband belt edge is 2.3% every nm on blue limit, is 1.9% every nm on red limit.It is identical substantially that the form of noticing the overall optical spectral curve is compared during with vertical incidence when 60 degree incidence angles.The spectrum of Figure 18 and Figure 19 is to use the polarised light parallel with TD (striding across the Web direction) to obtain.Though the refractive index of the thick pet layer of 1/4 wavelength can not directly be measured,, it is believed that they will equate approx with the refractive index of pet sheet layer.The refractive index of the latter in this example is to use a MetriconPrism coupler of being made by the MetriconCorporation of New Jersey Pennington to record.For stride across Web (by tentering or TD) direction, following Web (machinery or MD) direction (also being referred to as length orientation or LO direction) and thickness or z direction of principal axis have been measured refractive index.Is nx=1.674 to the pet sheet layer along the refractive index of TD direction; Along MD direction ny=1.646; And along z axle index nz=1.490.Isotropic index of Ecdel is about 1.52.PET can obtain by regulate its relative draw ratio along this both direction along the balance preferably of the refractive index value between TD and the MD direction.The delustring bandwidth of s-polarised light in the birefringence reflection multilayer film and size are increased with incidence angle, just as in the film of making of common isotropic material.Therefore, one very narrow transmission when the higher incidence angle will be punctured into zero bandwidth to the s-polarised light.This have only intensity just can weaken when the p-polarized component is constant owing to have only when the s-polarization fading, so can not influence the excitation of transmitted light greatly.To the transmission band of broad, s-and the difference of p-polarization in transmission have become of such little moment.

To on average will under typical ambient lighting conditions, observing of s-and p-polarised light spectrum.In various application, can advantageously use the different behavior of s-and p-polarised light.

B2.f-ratio

That can adopt special production has individual reflection tape cell classification heap layer and the extrusion equipment of design, can handle the f-ratio of blooming of the present invention and device, produces a plurality of zones of reflections that band leads to colour filter or is transferred to the spectrum special area.For example, can control f-ratio and produce and have the narrow green logical colour filter of high saturated transmitted colors, and only use a simple thickness classification heap layer.

When the intrinsic bandwidth that makes first harmonic (reflection potentiality) when reaching very big, (Q * Q) suppresses twice reflected harmonics in the unit of 1/4 ripple.Obtain one by the scope that changes f-ratio value to a special value and have the unit design of the higher intrinsic bandwidth that compares is once all arranged with the second harmonic zone of reflections, the design point of this and Q * Q differs greatly.An example of this system is a biaxial stretch-formed PEN/PMMA system, and its f-ratio is

$F_{\mathrm{PEN}}=\frac{D_{\mathrm{PEN}}\&times;N_{\mathrm{PEN}}}{D_{\mathrm{PEN}}\&times;N_{\mathrm{PEN}}+D_{\mathrm{PMMA}}\&times;N_{\mathrm{PMMA}}}=0.714$

With

$F_{\mathrm{PMMA}}=\frac{D_{\mathrm{PMMA}}\&times;N_{\mathrm{PMMA}}}{D_{\mathrm{PEN}}\&times;N_{\mathrm{PEN}}+D_{\mathrm{PMMA}}\&times;N_{\mathrm{PMMA}}}=0.286$

D herein _PMMA=46.7nm, N _PMMABe 1.49, D _PEN=100nm, and N _PENBe n _x=1.75, n _y=1.75 and n _z=1.50.When vertical incidence, will there be one to be about 8% first harmonic intrinsic reflection bandwidth and one and to be about 5.1% second harmonic intrinsic bandwidth.For the common situation of normal incidence, without the refractive index of z-direction.Therefore, for N _PENRefractive index along x-and y-direction equates, thereby uses this value.Therefore, if the multilayer of polymeric layer heap layer is designed to the broadband reflection device of making that thickness has linear gradient, and first harmonic and two subharmonic all have the strong reflection band, and then contiguous once also will form a passband filter with the secondary reflection band.If can regulating course right thickness, thereby when once the short wavelength band edge of band was about 600nm, then the result will form the passband in visible spectrum central authorities as shown in figure 20.This heap layer is to be designed to simulate-224 PEN/PMMA heap layer, its can as routine E1-1 described in by biaxial stretch-formed, so that the PEN layer can be provided n at 633nm _x=1.75, n _y=1.75 and n _z=1.50 refractive index.PMMA has and is about 1.50 isotropic refractive index.From the thinnest layer to, in the heap layer each follow-up layer to being designed to than a pair of thick 0.46% of front.If with a bigger gradient, such as be 0.63%, then the red zone edge of one-level band enters infraredly with regard to extending fartherly, and the red zone edge of two secondary peaks also can increase, and causes being shown in the narrower passband of Figure 21.

It is also noted that f-ratio value can be changed a little balance preferably once with the intensity of the stopband of second harmonic.Also have, the belt edge sharpening technique can be used for making passband edge edge sharpening (what use is that line style distributes) in these calculating ions.Suitable belt edge sharpening technique is described in No. 085 U.S. Patent application at the 09-006 of title for " blooming with sharpening belt edge ".The uniformity that strides across blank that so a kind of film is designed because nothing strides across blank multiplication error appearance than doubling design better such as the double-colored bag in routine E1-2 (two packet), is consulted routine B7-1 to make comparisons with E1-2 as striding across blank at an example of the variation of multiplication aspect of performance significantly.

Have been found that the multilayer film with certain distribution can produce than getable in the past and have the rapider spectrum spectrum that jumps to change.Fig. 1 shows the sectional view of a membrane structure, and it is not pressed yardstick and draws, but is that to have be helpful when describing the distribution of this requirement.As shown in the figure, multilayer film 120 includes 12 layers of respective layer of the series arrangement that replaces by two kinds of materials (" A " and " B " material).The optical material of three kinds or more different in kind can be used for other embodiment.Every couple of adjacent " A " and " B " layer are formed an ORU,, and finish with ORU6 from the backing down the beginning of film with ORU1, and these ORU have optical thickness OT ₁, OT ₂... OT ₆) these optical thicknesses are the same with item " Dr " in marking equation 1 in the above.At the wavelength of design, to the primary event rate (M=1 in equation 1) of maximum, the relative A of each ORU or one 50% f-ratio value should be arranged with respect to B.Can consider that the A layer has higher X-(in the plane) refractive index than B layer, this is because the former demonstrates thinner than the latter.ORU1-3 is incorporated among the multilayer heap layer S1, and the optical thickness of each ORU descends monotonously in negative-Z direction this heap layer.ORU4-6 is incorporated among another multilayer heap layer S2, and in this heap layer, the optical thickness of each ORU rises monotonously.This ORU distributions of optical thicknesses is depicted among Fig. 2.The spectrum transformation aspect that is distributed in the production sharpening as this thickness is helpful.Yet, before using the example of this preferable distribution, describe an example that does not make the bandpass optical filter of belt edge sharpening first.

Fig. 3 illustrates the design that the band is made up of 300 layers of respective layer nearly leads to multilayer film, from the top of film or the front begin then the physical thickness that gone out each respective layer film towards the bottom or the back displays of film.Begin to carry out towards the bottom or the back side of film then from the top or the front of film.Data point 122 representative has 1.5 refractive index materials planar and (for example, PMMA) puts 124 representatives and have in 1.75 the plane refractive index materials (for example, PEN).Layer numbering 1 and 2 constitutes " first " ORU, and 3 and 4 on layer constitutes the 2nd ORU, and the like.The optical thickness of a given ORU equals the optical thickness sum of its high and low index.Layer 1 to 150 constitutes first multilayer heap film S3, and layer 151 to 300 constitutes second multilayer heap film S4.Form the heap layer for these two a dull ORU optical thickness that descends is all arranged.The discontinuity on optical thickness at these two heap interlayers causes a simple recessed transmission band 126, is shown in Fig. 4.Fig. 4 is from the film of Fig. 1 and adopts Azzan and 4 * 4 matrix methods that Bashara summarizes calculate " oval symmetry and polarised light ", wherein supposed vertical incidence light and as the constant refractive index (no chromatic dispersion) of the function of wavelength.Have one with 126 and be about 60% transmission peaks, full width at half maximum 128 is about 50nm and by the centre wavelength that is about 565nm shown in 130 lines.Part bandwidth with 126 is a shade below 10%.In surpassing about 75% scope of visible spectrum, be 80% at least in the reflection.

Make spectrum that the extra play of the special optical thickness distribution of (cut-onandcut-off) transition effect be arranged straight up and down with providing to have, can make film with much smaller part bandwidth transformation.Fig. 5 has illustrated the design of this film, and data point 122,124 representative is shown in the same material of Fig. 3, has refractive index 1.5 and 1.75 respectively, and has as the identical grading linear thickness distribution in Fig. 3 with 150 series of strata row among the S4 at multilayer heap layer S3.The film of Fig. 5 has just added heap layer S5 and the S6 with constant substantially (non-graded) ORU of optical thickness between heap layer S3 and S4.The ORU of heap layer S5 has the optical thickness that equates basically with the minimum optical thickness of heap layer S3, and the ORU of heap layer S6 has the optical thickness that equates basically with the greatest optical thickness of heap layer S4.Same relation also is suitable for each constituent element of these ORU.The coaxial spectrum that illustrated heap layer is calculated is shown in Fig. 6, has pointed out much steep transmission band 132.The magnitude of straight minute bandwidth with 132 is 3% or littler.

Produced another kind of multilayer film, its design is shown in Fig. 7, improves the peak transmission and goes out steeper belt edge (narrower transmission band).This is to have used for data point 122,124 identical materials, and respective layer is aligned to forms among the multilayer heap layer S7-S10, as shown in the figure, wherein S8 and S9 have the thickness distribution of inverse curve mutually and the heap layer S7 of adjacent part and S10 have slight curving thickness distribution with respectively with the curvature coupling of heap layer S8 and S9, its crooked shape can be followed the functional form of any number; The main purpose of form is to prevent the strictness that appears at the thickness in the 1/4 ripple heap layer to repeat with the layer of being transferred to single wavelength.Adopting special function here is the additivity function of a linear distribution (with on one side identical of the short wavelength who is used in S7 long wavelength on one side and S10) and a trigonometric function, comes its distribution of bending with a suitable negative or positive first order derivative.An important characteristic is that the second derivative of the thickness distribution of ORU is positive to redness (long wavelength) belt edge of a reflective stack layer, and blueness (short wavelength) belt edge of a reflective stack layer is born.Note,, need opposite notion so if what involve is the belt edge of recess transmission band.The additional embodiments of same principle comprises having first order derivative multiple spot is arranged is that the layer of null value distributes.All scenario here, about those ORU distributions of optical thicknesses by reality come adaptive best-fit curve cause can comprise the optical thickness value less than 10% little statistical error.

Fig. 8 shows the coaxial transmission of the calculating of the film in Fig. 7.Peak value with 134 is more than 75%, and the part bandwidth is at the order of magnitude 2% or less.Calculated representing with curve 136,138 respectively to p-and s-polarization from the axle transmitted spectrum and in Fig. 9.Done incidence angle is 60% calculating and supposes that two types layer is that coupling is in refractive index 1.5 in out-of-plane refractive index.Attention is to the preservation of the high transmission peaks of p-polarization and little part bandwidth.Also to note the transmission peaks of s-polarization is disappeared.But, the transmission band that is arranged on the coaxial broad near infrared region now to s-and p-polarization all can be in Fig. 9 the red end of spectrum see.

Similar transformation sharpening technique can be used to have the broad transmissison characteristic such as high pass or optical low-pass filter multilayer film.Draw several such examples below, in certain embodiments, every layer the physical thickness that constitutes an ORU changes with the synchronised distance on transmembrane thickness, for example, change according to identical linear function, and in remaining embodiment, the variation of the thickness of the layer of an ORU of formation is different.High index of refraction and low-index layer have 1.75 and 1.5 refractive index respectively in each example below, and are dispersionless.

	S11	S12	S13	S14	S15
						Sum
	170	30	30	30	30

High index of refraction begins thickness (nm)	154.6	112.4	112.4	112.4	112.4
						High index of refraction layer thickness increment (nm)	-0.4965	0.726	0.726	0	0.726
Low-refraction begins thickness (nm)	183.3	133.3	133.3	133.3	133.3
						Low-refraction layer thickness increment (nm)	-0.5882	0.8608	0	0	-0.5882
Beginning ORU optical thickness (nm)	545.5	396.65	396.65	396,65	396,65
						ORU optical thickness increment (nm)	-1.7512	2.5617	1.2705	0	0.3882

The multilayer heap layer S11 that forms is as the design of baseline film., then film is made up earlier: S11+S12 (to the physical thickness distribution referring to Figure 10, and to reflectance curve 142 referring to Figure 11) single heap layer S11; S11+S13 (physical thickness is distributed referring to Figure 12, and to reflectance curve 144 referring to Figure 13); S11+S14 (physical thickness is distributed referring to Figure 14, and to reflectance curve 146 referring to Figure 15); And S11+S15 (physical thickness is distributed referring to Figure 16, and to reflectance curve 148 referring to Figure 17) does the calculating of coaxial reflectance spectrum 140.Arrive just as seen from Fig., it is that the heap layer (a heap layer S14), of zero thickness gradient only appends on the heap layer S11 with the heap layer (a heap layer S15) that the component of ORU has an opposite thickness gradient substantially that the heap layer (a heap layer S13) that have a heap layer with opposite thickness gradient (a heap layer S12), opposite thickness gradient and f-ratio value depart from, one have, and the acutance in the spectrum transformation is had the effect that progressively meets the requirements.

Principle above adopting does not need two groups or more groups of layer higher harmonics just can be utilized to be created in a plurality of zones of reflections of the visual field of spectrum.The design of the inhibition of various harmonic waves is used to produce various spectrum intervals and color.For example, compare, once can be adjusted to other by f-ratio value value and be worth and adjust with the relative peak heights of high order with a secondary peak at f=0.5.Harmonic wave luminous power when any f-ratio value can use tricks to get it right in the effective refractive index difference of known f-ratio value and harmonic number estimate to one good approximate, can insert it formula or only need do an adjustment to formula to the optical analog program of Q * Q (f=0.5) 1/4 ripple heap layer: pile layer (the f-ratio value through adjusting is arranged) when the spectral response of calculating one given time (order) and be taken as the heap layer with the availability indexes difference Q * Q that is shown in Figure 22 and handle, the number of supposing must multiply by the group number.Effective refractive index with respect to Q * Q heap layer is drawn by the curve map among Figure 22, function as f-ratio value, first harmonic has a maximum (Q * Q point) second harmonic and has two maximum, and the like, compare with a bandwidth, the high order bandwidth and the peak reflectivity of simple heap layer can be estimated from these numerical value.Owing to calculate the hypothesis that n high order peak reflectivity needs n times the number of plies, it is useful that the number of times that multiply by it with each high order curve repaints among Figure 22.This is illustrated in Figure 23.Some important f-ratio values can obtain from these figure.

For example, all evens all have zero reflection power when f=0.5, and all odds all have maximum when f=0.5.At f=0.167 and 0.833 maximum is arranged for the third time, and the 4th time at f=0.125 with minimum was arranged at 0.875 o'clock.Be 0 at f=0.33 and 0.66 o'clock reflection power for the third time, and the 4th time at f=0.25 with 0.75 o'clock be zero.In a pair of f-ratio value of back, maximum is arranged for the second time.F=0.2 and, first and the 4th time equal peak height is arranged at 0.8 o'clock.Also be like this for the second time and for the third time.Also having, at f=0.4 with 0.6 first and the 4th time equal peak height is arranged, also is like this for the second time and for the third time.Unillustrated quintic curve is at f=0.2,0.4,0.6 and minimum arranged in 0.8 o'clock, and at f=0.1,0.3,0.5,0.7 and maximum arranged in 0.9 o'clock.To a given film design, preferable f=ratio will depend on to be used and high secondary peak that selected hope will suppress or strengthen.

Except that heap layer design, material is selected advantageously to be used to regulate the higher hamonic wave bandwidth, and can not locked in the special interval between two reflection bandwidths.Right Q * intrinsic reflection the width of Q heap layer of given material layer equals the Fresnel reflectance factor of their interface approx, and it is only relevant with refractive index difference in the plane when vertical incidence.

Material selects can also to be used for producing film and other optical bodies that shows that reflectivity descends as a function of angle.Especially can use some combination of isotropism and birefringent layers, wherein the spectral contribution of isotropic layer has reduced the angle that tilts.These designs are discussed below.

Except the isotropism/birefringence heap layer combination that is described below, the design of other heaps layer also can be used to produce the film or the another kind of optical bodies that can show about the color transition of incidence angle in reflection, it is different from usually in known spectra dull through shifting to those of short wavelength's making.For example, a kind of combination of three materials can be used for suppressing the p-polarised light an angle but not in the higher hamonic wave of another angle.Can obtain similar effects for the s-polarised light with two-layer design.

If will seek out the film of the pure especially color of demonstration and optical bodies (such as, for example, a herring bone reflector), big or little f-ratio value can be used for limiting intrinsic bandwidth, so need extra play to obtain with the available identical reflectivity of the heap layer of a Q * Q.(0.5 f-ratio value being arranged by definition Q * Q heap layer) similarly, making a broadband reflection device with steep belt edge can be with big or little f-ratio value, and have the layer (for example, 1000 or more) of suitable thickness gradient and/or show that the material of big refractive index mismatch can make the reflection envelope fill up with a large amount of.In other words refractive index difference limits intrinsic bandwidth and the increase compensate for brightness loss of the number of plies in the less plane.

In the above in the design in special applications, can make a ultraviolet reflecting film, it does not almost have in arbitrarily angled visible region at spectrum or not reflection, but in the ultra-violet (UV) band near 400nm, it is keeping the zone of reflections of a broadness at a big angular range.This is that arrangement layer is become in two membrane stack layers or the bag in (ultraviolet and an infrared heap layer), it is once that this ultraviolet wraps in the ultra-violet (UV) band, and this infrared bag designs to such an extent that can demonstrate the reflection peak of a high order in the ultra-violet (UV) band of spectrum, and it has demonstrated a maximum on reflectivity when the inclination angle.When incidence angle departs from vertical and when changing, then a ultraviolet peak moves to short wavelength, the high secondary peak that does not suppress that comes from infrared bag has moved into ultraviolet.

In other application, film of the present invention and optics can add one or more dyestuffs so that the absorption band of the zone of reflections of film and dyestuff is consistent at least when an incidence angle.Because the absorption band (or several absorption band) of dyestuff is unlike the zone of reflections of film, generally can not move with incidence angle, so this film will show a kind of color on the angle that the zone of reflections and absorption band meet, but after the two separates, will demonstrate one or more different colors on other angles.Can make absorption band in the optical stack layer under a given incidence angle consistent on the contrary with certain transmission band.Like this, can be for example when vertical incidence this film be black, but passband will not move on to and can be covered short wavelength by dyestuff spectrum when the angle of inclination, so that this film will become will be coloured.Copper Pthalocyanine pigment has quite steep spectral signature at visible light, therefore is particularly suitable for this embodiment.

In other embodiments of the invention, can combine film of the present invention and optics and one or more top rake glass prism.In a special embodiment, a top rake glass prism bar and a film combine can watch coloured mirror film on the angle except the spectrum angle.The trade trade mark that can buy from the 3M company of Minnesota State St.Paul for placing adjacently such as the microprism material of (OptieaLightingFilm) or coupling light to multilayer film with multilayer film.The film of this stratification is in the different color of different angle transmissions, and because prism changes direction of light, so these two can combine and make people to see a kind of color at a given angle place, and if prism is not redirected to the observer to light, so generally can't see it.In addition, if prism and film optically are coupled together, it can change the angle of the light transmission being advanced film, therefore, has changed color at that point.This film demonstrates a three-dismensional effect, wherein, on non-spectrum angle, can see coloured level crossing it also with prism with without change in color of interregional generation of prism.

In also having a kind of embodiment, film or an optical bodies with the spatial distribution on pinnacle is used as first element, second element combination that constitutes with coloured mirror film by a broadband, it is the effect of pinnacle light source that first element has the wideband light source that changes this film that is used for throwing light on, and therefore produces more strikingly color in coloured mirror film.Unusual sensitive colour switching has been found that with the color change of pinnacle light illumination inteferometer coating to produce to angle in order to produce.

In various embodiment of the present invention, the effect that the device that can give to obtain at last with the elimination of halation color is decorated.For example, can place like this, make film parallel at certain several point according to two films that the present invention makes, but not parallel at other point, perhaps make coloured mirror film and can make up with a broadband mirror film according to the present invention.If film has complementary colours, or a slice in the film is broadband mirror film and another sheet is coloured mirror film, and the combination that then obtains at last will change or offset the color in certain several place of top layer film, but do not change in other place or offset.

B3. Zu He isotropism/birefringence membrane stack layer

The design of some optical stack layer can be used to produce the color transition relevant with incidence angle, it be different from those by a known spectra with angle towards the dull color transition that is produced that moves of shorter wavelength.Especially, multilayer of the present invention heap layer can combine to produce some unusual angular effects with the multilayer heap layer of prior art.For example, can be to the birefringence Coloured film that has one or several center to penetrate when the vertical incidence of the present invention in the transmission at setted wavelength place, with one when the vertical incidence heap layer at those given wavelength place isotropic layers do not cover coextrusion or stacked.So the object that is made up looks when vertical incidence and to resemble the mirror that has plated.But when the angle that tilts, isotropic membrane will leak the p-polarised light, and the transmission peaks that allows birefringent film becomes coloured minute surface at visible-range when high incident angle.This supposed the reflection bandwidth of birefringence heap layer extend enough far enter infrared, to stop all ruddiness when the oblique angle.To or isotropic membrane stack layer of having Brewster (Brewster) angle when an angle of elevation this maximum effect will appear.Also can design the transmit red light that birefringence piles up the oblique angle.

A variation of top designing technique comprises the birefringence heap layer that has more than a spectral band-width, and wherein, not all passband is all blocked by isotropic reflective stack layer.These goods do not have silver color when vertical incidence, and will change to another kind of color from a kind of color from vertically to the oblique angle time.

On the contrary, can select to make some to have the material of z-refractive index mismatch.Wherein, have the material of refraction in the higher plane, its z-refractive index is minimum.A kind of combination like this is PEN/PETG.If be higher than 120 ℃ of stretching PETG, it has one to be about 1.57 isotropic refractive index, if the stretching PEN that describes in by routine E1-1 has $n_x\&cong;1.75,n_y\&cong;1.75$ With $n_z\&cong;1.50.$ These layers all will demonstrate the reflectivity of increase to two kinds of polarised lights when the oblique angle, so, if use separately or combine, can be designed to the film that obtains at last to show when the vertical incidence coloured with z-refractive index matching layer, and demonstrate silver color constantly at the oblique angle.Have and be higher than 1.55 indexes, other copolyester and Merlon be to be used for combining to obtain the suitable material of this effect with PEN.Though it is colourless combined films to a visual angle at least that top example relates to making, can be with these identical designing techniques to draw uncommon color transition (decorate, secret grade is wanted)

B4. blue the transformation

Can make some film of making according to the present invention, in the unit, comprise those of the negative birefringent layers of single shaft such as those, be used for showing blue the transformation (in other words, when incidence angle changes, spectrum peak is to moving that the orchid of spectrum is held), it is significantly greater than viewed with common colour shifting film.In addition, because to given (non-perpendicular) incidence angle, will be for the blue amount that changes of p-polarised light than viewed greatly with common film, will be bigger with respect to the difference of the color transition of incidence angle than the difference of conventional film to film of the present invention.This characteristic of back makes the color transition of making in film of the present invention that more noticeable effect be arranged, and this makes them be more suitable for the color transition demonstration again.

In any membrane stack layer, the amount that changes with the blueness of incidence angle can push away from the tuning formula of fundamental wavelength respective layer

L/4=ndcos θ formula B4-1 L herein is that θ is that the incidence angle n that measures outside vertical in that layer is the effective refractive index of the polarised light that passes through this layer of material layer along given direction to the tuning wavelength of given layer.And d is the physical thickness of layer.In isotropic membrane stack layer, have only the value of cos θ to reduce with the θ increase.But in single shaft negative birefringence film of the present invention, cos θ increases with θ for the p-polarised light and reduces.When a unit for example comprises one or more layers single shaft negative birefringence material or twin shaft birefringent layers, form by PEN or PET, wherein, the p-polarized light detection measures a z-refractive index rather than the value in the higher plane of refractive index just, the result higher incidence angle obtain one descended effectively cause refractive index.Accordingly, the effectively low z-refractive index that is caused by the negative birefringence layer in the unit has caused the transformation of a secondary blueness to append in the blueness transformation that appears at the thin heap layer of isotropism.Compare with the membrane stack layer that is made of isotropic material fully, melange effect causes the bigger blueness of spectrum to change.The blue value that changes will be changed the thickness weighted average of incidence angle in L by all material layer in the unit.Therefore, blue transition energy is by being adjusted in the unit birefringent layers relative thickness of isotropic layer is strengthened or weakening.Maximum blue the commentaries on classics claims to adopt in all layers of heap negative single axial birefringence material to reach in this f-ratio value level crossing that will cause must at first considering in product design.

On the other hand, refractive index will exceed much in its plane of the z-of one of layer material that replaces in film refractive index ratio, and another material is when having low birefringence, to its delustring band of p-polarised light along with the variation of angle is just shifted to blueness with lower speed than s-polarised light in belt transect, therefore, minimum blueness changes by only adopting single shaft positive birefringence material just can reach in the optical stack layer.

For polarizer, use biaxial birefringent material, but for incident light when birefringent film shakes this simple case of main shaft of device, its analysis is all the same with the twin shaft birefringent film for single shaft.To the direction between two main shafts of polarizer, this effect still can be observed, but analyzes more complicated.But in general, for the light of the azimuth incident between two main shafts, the blueness of transmitted spectrum changes will a value, and it is between the blue transformation value that obtain of incident light in two optical axises of film.To the polymer film that great majority have been orientated, optical axis is consistent with the tensile axis of film or vertical with it.

For make with PEN along two main shafts of film mirror film with high draw ratio, adopt the condition that is similar in the example given below, the plane of PEN layer/z-axle folding rate difference is about 0.25 (1.75-1.50).This refractive index difference is less than the film (about 1.66-1.50 in other words) based on PET.For polarizer based on PEN, make light incident like this, its plane of polarization is along extinction axis, this effect even more remarkable.Because the z-axle refractive index of the difference of refractive index and PEN specific energy much bigger (being exactly to be, about 1.85-1.50) mutually in the PEN plane is so cause having bigger blueness to change for the p-polarised light than observed in biaxial stretch-formed multilayer membrane stack layer.

If only with single shaft positive birefringence material, perhaps it is then compared blue transformation with the isotropism blooming and will be weakened together with isotropic material in the heap layer.If the p-polarised light is wished that in all incidence angles high reflectivity will be arranged, then the difference of the z-refractive index of two kinds of materials.Must will be example with a single shaft positive birefringence material basically less than refractive index difference in the plane, such as the syndyotaxy polystyrene of biaxial orientation, it has refractive index in the plane that is about 1.63 z-refractive index and is about 1.57.Other material may be to have the isotropic coPEN that is about 1.63 indexes.

B5. colour saturation

Just as noted, particularly comparing with isotropic multilayer film of prior art, birefringence colour shifting film of the present invention demonstrates the colour saturation of improvement.When (for example, glancing angle) increases the visual angle by film from the vertical angle to the oblique angle, the multilayered color-forming shifting film with isotropic refractive index on their excitation, degenerates (to transmission and to reflect all is like this).This part is this relatively poor fact of efficient owing to the reflection of the random polarised light of part (p-polarised light) when the angle of propagation by film increases.Therefore, depart from vertical at the angle and when shifting to shorter wavelength, the zone of reflections also is weak, allows unwanted spectral component damage whole transmitted spectrums when the zone of reflections.When film is embedded in glass by bonding prism or has refractive index when being higher than other medium of 1,0 significantly, problem is with regard to especially severe.

On the other hand, plurality of layers of double refraction colour shifting film of the present invention can be kept their colour saturation along with the increase at visual angle, as long as optical layers is suitably mated along the refractive index of z-axle (perpendicular to the axle of membrane plane).Below the example calculation that the increase with the visual angle of isotropism multilayer film and birefringence multilayer film is changed the situation of color and colour saturation is shown in.Excitation can increase when the narrow one-tenth of bandwidth pinnacle.But, can be weakened by the broadband reflection of air/polymeric surface layer interface from the excitation of the polymer multi-layer heap layer light that reflects.Wish in this case on polymer film, to provide disappear the reflection cover layer show.

Example B1-1 and B5-2

Alternating layer by materials A with refractive index Na=1.75 and Nb=1.50 in the plane and B is constituted, and be designed to when vertical angle, to provide saturated " blueness " transmitted spectrum (if with uniform white illumination source) 80 layers of optical stack layer transmitted colors its calculate as spending to 80 functions of spending angles from 0.Utilize the CIEx-y chromaticity coordinate and the La*b colour space to calculate transmitted colors, to each colour system, when the chromaticity coordinates value from the color value of light source (to La*b be (0,0) and to x-y system (0.333,0.333)) when removing, colour saturation increases.

To each chromaticity coordinates system, a multilayer system has been done the comparison of color value for the visual angle, this system along z-axle refractive index is $n_z^a=1.75,n_z^b=1.50$ (routine B5-1, isotropism, z-refractive index mismatch situation) and $n_z^a=1.50,n_z^b=1.50$ (routine B5-2, z-refractive index coupling, birefringence situation).Can make the PEN/PMMA heap layer that is similar to latter event.It the results are shown in Figure 24 and 25.As seeing in these figure, the birefringence of routine B5-2, z-refractive index matching system have HI SA highly saturated angle of elevation color value and the isotropism system of routine B5-1, have the colour saturation of violent decline along with the increase at visual angle.

B6. spectrum definition

Though the frequent f of the present invention describes the visual field about spectrum here, but various embodiment of the present invention just can be used for operating down at the different wavelength (thereby frequency) of electromagnetic radiation by the suitable adjusting of various parameters (for example, the selection of the optical thickness of optical layers and material).

Certainly, for most of interested materials, a change that important effect is refractive index and absorption coefficient of wavelength shift.But the principle of refractive index coupling and mismatch is to still being applied to each interested wavelength, and can be used for be an optics selection material that will operate on a specific region of spectrum.Therefore, for example, suitable contract in proportion and size can operate in infrared, the far ultraviolet of spectrum and ultraviolet region.In these cases, the also scaling in proportion approx about the optical thickness of refractive index and optical layers under these operation wavelengths with wavelength.Even more electromagnetic spectrum can be utilized, and comprises very high frequency(VHF), hyperfrequency, microwave and millimeter-wave frequency.To show the polarization effect with suitable scaling in proportion, and refractive index can obtain from square root by medium function (comprising and imaginary part) to wavelength.In these long wavelength bands, useful product can be minute surface reflective polarizer and part polarizer.

The zone of reflections is defined reverberation bands of a spectrum that are limited to both sides by the wavelength region may of low reflection usually.With in the application of medium stacked layer, it generally is low to the stage that is enough to ignore absorbing many, and definition provides with transmission.In those terms, the zone of reflections (or stopband) is generally defined as a low transmission area that is limited to both sides by high transmission area.

In a preferred embodiment, the continuous spectrum that the single zone of reflections (or stopband) of p-polarised light is had between any two wavelength (its transmission is greater than 50%) in succession, and comprise these wavelength in succession as end points, and the average transmission from an end points to another is less than 20%.This preferable zone of reflections (or stopband) is described non-polarized light and the only same method of vertical incidence.But, calculate with a kind of method for the transmission value in the description in front of s-polarised light, it does not comprise by with the top layer of heap layer or heap layer or this part light of tectal air interface reflection.To these preferred embodiments, bandwidth is defined in the distance between two wavelength in the band, makes the unit with nm, each of these two wavelength all with 50% transmission on the most close in bandwidth, it is transmitted as 10%.In normally used term, bandwidth is defined by 10% transmission point.Corresponding blue and redness (short wavelength and long wavelength in other words) then belt edge just get the wavelength at 10% transmission point place defined above.The transmission of preferable stopband is taken at the average transmission between 10% transmission point.

The belt edge slope of the stopband of describing in the paragraph is taken from transmission/wavelength points of 50% and 10% in front, and provides with the percentage unit of being transmitted as of every nm.If the zone of reflections does not have the bandwidth that sufficiently high reflectivity satisfies preferred embodiment and the definition of belt edge slope, bandwidth just is expressed as the big full duration of reflectivity half-shadow so.

Passband is generally defined as the spectral transmission band that is limited by low relatively transmitted spectrum district.For the multilayered color-forming shifting film, the passband stopband that is reflected is limit.The width of passband is in the full duration at half maximum place (FWHM) value, and the belt edge slope is that 2 on the belt edge of a known the most close peak transmission point calculate, and their transmission value is 50% and 10% of a peak transmission value.

In a preferred embodiment, passband has a transmission band, and it all hangs down transmission area on the both sides of transmission peaks, the transmission value that the minimizing low transmission area of transmission is a peak transmission point 10% or littler.For example, in this preferred embodiment, passband with 50% transmission maximum will be had 5% or the lower minimizing zone of reflections of transmission be limited in both sides.More preferably, the both sides transmission minimum of passband is less than 5% of the peak transmission value of passband.

To passband, its belt edge slope is preferable greater than every nm about 0.5%, and is then best when its belt edge slope is better its slope greater than every nm2% approximately greater than every nm1%.

B7. non-polarized colour filter

About the s-polarised light, the bandwidth of the birefringence membrane stack layer of here describing and reflectivity all increase with incidence angle with same form with common isotropic material.If, select suitable refractive index materials, p-polarization luminous energy is produced identical effect.In that example, the spectrum that can make s-and p-polarised light is with similarly or even show as the function of an incidence angle in the same manner.To going through of this exercise question, consult United States Patent (USP) the 5th, 808, No. 798, the multilayer film of Miao Shuing has a sizable z-refractive index mismatch there, and symbol is opposite with refractive index mismatch in the plane.Phenomenon there and filter bandwidth and reflectivity are irrelevant.Though can buy material to obtain this effect, it is limited that but the selection of the compatible material of good ply adhesion can be provided, and in the selection of material, people must sacrifice the size of refractive index difference in the plane usually, to obtain required z-refractive index difference.

We find then that again the birefringence multilayer heap layer with relatively little z-refractive index mismatch can play a part unpolarized colour filter in some special case.In these examples, one of belt edge of the zone of reflections of the Q of simple classification * Q heap layer (short wavelength side or long wave limit) will be by unpolarizedization, but be not both sides.Some colour filter, such as, for example, what blueness or cyanic colours transmitting filter can have them enters into dark heat red zone edge enough far away, and the polarization effect there is inessential to desired application.If utilize computer optimization to regulate one-tenth-value thickness 1/10, one or two belt edge of the membrane stack layer of the approximate z-refractive index coupling that has at the interface place of two or more materials so can be accomplished that unpolarizedization reaches superior degree in isotropism membrane stack layer.Provide two examples of birefringence heap layer below, they demonstrate the unpolarizedization effect basically in their blue ribbon edge, and simple layer thickness profile is arranged.These membrane stack layers will have prior art that important improvement can be provided to unpolarizedization color splitter.Its example is provided by L.Songer, sees " PhotonicSpectra ", the 88th page of November in 1994.Five layers of ABCBA optical repeat unit heap layer of Songer are designed being in the BK-7 glass at 37.5 degree and work, and its refractive index is about 1.52.

Example B7-1

The PET/Ecdel film of 417 layers of coextrusion is shown in Figure 26 to the transmitted spectrum of s-and p-polarised light." Ecdel " is a kind of polyether ester that can buy from Estman Chemicals.Two spectrum are all taken from aerial 60 degree incidence angles, and it is equivalent in refractive index is 1.52 glass about 35 degree angles of (such as for example, BK-7 glass).This multilayer film is by making described in routine E1-2.As described in that example, the process that is used for making this multilayer sample has been utilized asymmetric two times of multipliers.It doubles the number of plies of producing in feeding device.Design multiplier to such an extent that make two groups of layers be adjusted to reflection wavelength band separately, the wavelength place that is separated is being compared at their center by multiplication.But multiplier is not being crossed over all strict identical multiplication ratios of some generation of melt-flow.Especially, near one or two edge of film, on ratio, usually have a considerable variation.For convenience, the sample of this example is taken near the edge of the film of describing in routine E1-2.The position that B1-7 strides across blank is approximately from the Ban Michu that strides across the blank position of the spectrum that obtains routine E1-2.In the position that strides across blank on film of routine B1-7, multiplication is than greatly reducing, and the reflection that two zones of reflections have merged into single broad substantially is wide.In Figure 26, notice the s-of close 525nm and the belt edge of this single band of p-polarised light are overlapped within 10nm, and be separated about 40nm near 800nm place red tape edge.The s-polarised light is depended mainly on the interface of the polymer/air of film at the transmission value that is lower than 500nm and be higher than 700nm, and can improve, or imbed a high refractive index medium such as being bonded between two glass prisms with the reflection cover layer that disappears.For p-polarised light (500nm is to 710nm), the average transmission of stopband is about 6%, and in this example, the slope of all belt edge is about every nm2.5%.

For the p-polarised light, the reflection of routine B7-1 has several significant spectrum leaks, and on average is transmitted as 6% from 500nm to 710nm, and this example is only for the unpolarizedization belt edge of this optical stack layer of explanation.The people who is familiar with this area can easily produce the width reflection belt filter that is made of PET and Ecdel, it on the bandwidth of whole stopband transmissive on average less than 5% or even less than 2%.The spectrum of Figure 26 is to use polarization parallel to obtain in the light of TD direction (in this example, also being referred to as the x direction).The refractive index of the pet sheet layer that measures is n _x=1.666, n _y=1.647, n _z=1.490.Low-index material is Ecdel, and the refractive index of Ecdel is about 1.52.

Example B7-2

Second example with the birefringence heap layer at unpolarizedization blue ribbon edge is indicated in routine 1-1, and it is the multilayer heap layer of a PEN and PMMA.Attention coincides together at nearly 410nm place substantially to the belt edge edge of the transmission spectrum of s-and p-polarised light in Figure 38, and the red tape edge of close 600nm then almost is separated 40nm.In this example, the z-refractive index of PEN is reasonably well to mate with the refractive index of PMMA, and both are about 1.49 when 700nm.PEN has the chromatic dispersion more higher than PMM, by 400nm's $\mathrm{nzPEN}\&cong;1.53,$ And $\mathrm{nPMMA}\&cong;1.51.$ Within stopband, be 1.23% to the average transmission of p-polarised light.When 60 spent, the red zone edge slope was about every nm4.2%; And the blue ribbon edge slope is about every nm2.2%.The red zone edge slope is about every nm5.5% when vertical incidence.

Obtain unpolarized effect with the birefringence heap layer with z-refractive index matching condition, this optical stack layer also must guarantee high reflection, causes the p-polarised light of undesirable wavelength to have only several percentage points or still less can be by transmission.Will be when the s-polarization than p-polarization reflex time more consumingly, this is essential, owing to will be very different when the high incidence angle to two kinds of polarization Fresnel reflectance factors.Within the zone of reflections of unpolarized colour filter, the average transmission under the design corner of nominal is preferable less than 10%, less than 5% less than 5%, less than 2% the best.To good chromatic rendition, preferably belt edge demonstrates high slope.Steep belt edge is obtaining saturated also desired the obtaining of high-purity color.Slope is that every nm about 1% is preferable at least.Better greater than every nm2%, every nm is about 4% the best.Obtain with belt edge, can utilize computer optimization to get thickness distribution, or frequency band sharpening thickness distribution is applied to thickness distribution design.

Do not want to be bound by theory, the coincidence of two example Smalt belt edge that provide in the above think owing to the combination of the different bandwidth of s-and p-polarised light and to those polarizations with the different spectrum rate travel of having of spectrum angle.To the s-polarised light, when incidence angle when zero increases, the part bandwidth increases.P-polarised light part bandwidth is not changed with angle, because make z-refractive index coupling produce a Fresnel reflectance factor that has nothing to do with angle to each interfacial angle, but as described above, entire belt is allegretto shifted to blueness than s-polarization to same frequency band.These two effects are almost offset at the place, limit of frequency band orchid, and the result of generation is that blue ribbon edge edge remains under all incidence angles near conforming to.In redness on one side, these two effect additions make the belt edge edge separate s-and p-polarised light.The red zone edge that obtains at last becomes the average of two figure, on one side cause in this example non-polarized light being had lower slightly excitation in redness.

In other words, when the refractive index height is a lot of in its plane of the z-of one of membrane material that replaces in film refractive index ratio, and another material has low birefringence, then to the delustring band of p-polarised light along with the variation of angle is shifted to blueness to identical frequency band with slightly low speed than s-polarised light.A kind of membrane stack layer non-polarized light like this can be used for keeping a steep belt edge on red one side of a delustring band, such as, for example, unpolarized yellow and red transmission filter.Available to material f-ratio value adjusting or the mismatch of regulating the z refractive index regulate the blueness of s-and p-polarised light or the aligning at red zone edge subtly.

The f-ratio value of membrane stack layer can be conditioned the belt edge of the s-and the p-polarization of helping to aim at refraction band of the present invention.At 1000nm to PEN: a PMMA1/4 ripple heap layer (n _1x=1.75, n _1z=1.50, n _2x=1.50, n _2z=1.50) particulars below supposing are, when vertical incidence 0.5 f-ratio value being had layer thickness is d ₁=142.86nm and d ₂=166.67nm can calculate the function of belt edge as the incidence angle position.Height and low belt edge are at 953nm and 1052nm when vertical incidence.The belt edge displacement of p-polarised light is bigger than s-polarization, is like this to high belt edge especially.The frequency band of p-polarised light is from the 99nm stenosis to 73nm and the frequency band of s-polarised light is widened 124nm.Estimate this result in intermediate angle, just produced the data among Figure 27.

This illustrates a width that reduces to p-reflection of polarization band, if but the belt edge value map with the inverse of wavelength, then the bandwidth of p-polarization band can remain unchanged.Also notice, when s-and p-polarised light strictly not being mated in low wavelength belt edge on one side, under 60 degree, in air, the only about 10nm of difference, this application to many unpolarized colour filters is enough.P-polarised light belt edge is shifted to blueness really further than the corresponding belt edge of s-polarised light.The behavior that this and isotropism 1/4 ripple are piled layer differs very big.

Utilize n _1x=1.75 and n _1z=1.75 and n _2x==1.50 and n _2z=1.50, also an isotropic heap layer is calculated.F-ratio value to 10,000, its layer thickness are the diagrammatic sketch as a result 28 of d1=142.86nm and d2=166.67nm.High and low belt edge is at 953nm and 1052nm when vertical incidence, the same with anisotropic material.The belt edge of p-polarised light is with angle stenosis significantly, and the belt edge of s-polarised light is then the same with anisotropy.The band of p-polarised light is then widened 124nm from the 99nm stenosis to the frequency band of 29nm s-polarised light.The center of i band is identical to s-with the p-polarised light, and to anisotropic material, the center of p-polarization light belt reduces manyly than the center of s-polarization light belt.At 60 degree, in air, the belt edge of s-polarised light and p-polarised light is at interval greater than 30nm.When the refractive index difference of isotropic material increased, the belt edge of s-polarised light and p-polarised light also increased at interval.50nm's is typical at interval.For example, referring to L.Songer, " Phogonics Spectoa ", in November, 1994, the 88th page.

Compare with the displacement of s-polarised light, the relative displacement of p-polarised light belt edge is to be subjected to the influence that the quantity of birefringent material in the heap layer also has their absolute birefringence value substantially.For example, the f-ratio value that increases PEN/PMMA heap layer will increase the relative populations that has in the plane 1.75 refraction materials, also can cause a little blue displacement in the zone of reflections of s-polarised light.For one 0.75 f-ratio value, and use n _1x=1.75 and n _1z=1.50 and n _2x=1.50 and n _2z=1.50, and layer thickness is d ₁=214.29nm and d ₂=83.33nm, its height and low belt edge are at 967nm and 1037nm place when vertical incidence.As shown in Figure 29, this frequency band is wide unlike Q * Q heap layer.Also have, to the s-polarised light, belt edge is littler than the displacement of the belt edge of p-polarised light with the displacement of angle.To 52nm, and the frequency band of s-polarised light is widened 86nm to the band of p-polarised light from the 70nm stenosis.Though this heap layer design can not provide unpolarized filter, it will cause one than the bigger color transition with angle of Q * Q (f=0.5) heap layer.

The heap layer of a same material is in the opposite direction promoted f-ratio value will be made the blue ribbon edge of p-polarization spectrum will be aimed at the s-polarization spectrum.Be about under 0.25 the f-ratio value at one, these two almost overlap.To one 0.25 f-ratio value, thickness is d ₁=71.43nm and d ₂=250.00nm.High and low belt edge is at 967nm and 1037nm when vertical incidence, to f-ratio value=0.75 too.Because it is constant to have 1.50 z-refractive index materials amount, so the displacement of p-polarised light belt edge is identical to f=0.75, but the displacement of s-polarization band is bigger.To this heap layer, low wavelength band edge dislocation all is identical to s-polarised light and p-polarised light.To 52nm, s-polarised light frequency band is then widened 91nm to p-polarised light frequency band from the 70nm stenosis, and it the results are shown in Figure 30.

Big reduction with the f-value provides the belt edge coupling of s-polarised light and p-polarised light to have the shortcoming of the total reflection power that reduces the heap layer, is illustrated in Figure 22.Another method that the coupling at s and p blue ribbon edge can be provided in all incidence angles is to introduce mismatch aspect the z refractive index.If the PET of z-refractive index that supposes to have refractive index in 1.66 the plane and 1.50 is in the heap layer that replaces, second kind of material has 1.45 isotropic refractive index, and we see that from Figure 31 the low wavelength band edge of s and p overlaps substantially under all incidence angles.Even the z-refractive index is do not match (Dz=0.05), and refractive index difference is less than the isotropic heap layer (0.21 pair 0.25) as illustrating among Figure 28 in the plane, and p-polarization band has kept the bigger bandwidth of a ratio when isotropism when 90 spend in this example.In other words, the thin heap of this design layer is keeping unusual reflectivity under all incidence angles, and can be used for having the application of the colour filter aspect of high brightness and good colour saturation.The s that overlaps and the identical result at p blue ribbon edge can obtain with the birefringence PEN/1.45 isotropic refractive index material heap layer of a simulation.These situations are with introducing the example that controlled z refractive index mismatch improves film properties.Have 0.5 times of the same big membrane stack layer of refractive index maximum difference in Dz and the plane and also can satisfy the requirement of many colour filters.

The coincidence of s-and p-polarization spectrum Smalt belt edge is an important characteristic of the colour shifting film that here discloses, and is to have the purposes that exceeds unpolarized colour filter.The coincidence of s and p belt edge enable to make have one with the visual angle colour shifting film of color change, and also can make and have certain high colour filter of excitation.In a preferred embodiment, it is preferable that s-and its belt edge of p-polarization are less than 30nm at interval, and it is better being less than 20nm approximately, and it is best being less than 10nm at interval approximately.

In the application of equal bandwidth required to s that coloured light is arranged and p-polarization and reflectivity, the unpolarized colour filter of narrating above is useful as the look beam splitter.Especially these films can find the application as colour filter in the color separator of three prisms, and the 5th, 644, describe by the relevant lcd projection systems of No. 432 United States Patent (USP) by Doany for this type look separator.The structure of a special recommendation of these films in the color separator of that type is that session is mapped to earlier on the red reflex film (cyan transilluminator), and then is mapped on the film (blue transmission device) of reflection green and redness.Blue light is by two membranes and be mapped on the blue liquid crystal display light modulator.By the described preferable incidence angle on glass prism of Doany is 30 degree, and the present invention can provide this angle at an easy rate.For the various typical incidence angles that are applied in the glass is 30 degree, 35 degree, 37.5 degree and 45 degree.These angles are with reference to the central ray of light cone.Semi-cone angle may be 5,10,15 or even 20 degree, depend on the f number of optical system.As an example, in a system of cone angles with 15 degree, the beam splitters of placing for 35 degree incidence angles will run on the membrane stack layer from 20 spends to the incidence angle of 50 degree.

C. process detail

C1. technology is considered

The technology that is used for making coextrusion polymer multi-layer blooming of the present invention will change with selected resin material and the desirable optical property of the film that in the end obtains product.

To the resin of moisture-sensitive should extrude preceding or when extruding in addition drying in case retainingization.Can accomplish this point with any method well known in the prior art.A method of knowing is to use stove or the more senior heating in vacuum and/or the funneling drying machine that dries, and when extruding moisture is removed from resin.When funneling drying machine or furnace dried, dry time and temperature should be limited with solar heat protection degenerates or bonding.In addition, with should be sloughed moisture to the resin of the resin coextrusion of moisture-sensitive and damage coextrusion resin moisture-sensitive to prevent the entrained moisture of this resin.

Extrusion condition will be selected, to transport the fluoropolymer resin feed streams with continuous, fusion reinforced suitably with stable manner, mixing with pump.Last melt-flow temperature is chosen in such scope, will avoid solidifying at the low side of this temperature range, crystallization or unsuitable high drops, and degenerate high-end will the avoiding of this temperature range.For example, PEN (PEN) will down use last warm area (or happy and harmonious temperature) vacuum charging to extruder in dry 8 hours at 135 ℃ then, and scope is better between 270 ℃ and 300 ℃ of degree, and is then better between 275 ℃ and 290 ℃.

The polymer that preferably makes all enter feeding device (feedblock) is in identical with melt temperature or closely similar temperature.If two kinds of unmatched polymer of desirable melt processing temperature will carry out coextrusion, this just may require technology compromise.For example, polymethyl methacrylate (PMMA) generally pushes between the temperature of 235 ℃ and 250 ℃.But, be surprised to find that the melt temperature of using PMMA up to 275 ℃, PMMA can with the PEN coextrusion, consider to reduce to minimum as long as in the fusion sequence (train) of PMMA, do design, and in the molten stream of PMMA, whole holdup times are remained and make under the minimum will melt the possibility that occurs stagnation point in the stream.The result of (stagnation) point of remaining in a standstill is, the where is it wedge angle, and polymerization logistics where just has the tendency of delay.Found that in this respect another useful technology is exactly to start PMMA fusion sequence under conventional processing temperature, just when developed good molten stream in whole technical process, ability rises to the compatible temperature of higher PEN to the temperature of fusion sequence then.

On the contrary, can reduce the processing temperature of PEN, so that it is matched the melt processing temperature of typical PMMA.Therefore, be surprised to find that also that the fusing point of PEN (thereby its processing temperature) can add in the PEN polymer by comonomer and reduce, this has the very little reduction of following can for the ability of PEN drawn form dielectric grid.For example, have been found that with DMIP (DMI) and replace 2 of 3mol%, the birefringence of the PEN EVA that 6-naphthalene diformic acid dimethyl ester (DMN) monomer is made 0.02 unit that only descends, and glass transformation temperature only reduces by 4 or 5 ℃, melt processing temperature then descends 15 ℃.A spot of in this respect dimethyl terephthalate (DMT) (DMT) or other diacid or glycol comonomer also are useful.The also ester of available diacid comonomers or diester.Comonomer add to getting well of PEN polymer be in be entitled as " comonomer of change and the laminated reflective film of improvement " the 09/006th, more comprehensively narration is arranged in the 09/006th, No. 468 U.S. Patent application of No. 601 U.S. Patent applications and " optical device with dichroic polarizers and multi-layer optical film ".

The people who is familiar with this area obviously understands, can usefully use PEN processing temperature by copolymerisation to reduce and the combination of rising PMMA melt temperature, a kind of as using, another kind of or two kinds of technology and also having a kind of combination of technology by technological design.Equally, similar technology can be used the equitemperature coextrusion in the combination in the polymerization of PEN and polymer, PMMA and the polymer except PEN except PMMA or two examples all is not included in.

Be connected on extrude after, then undesirable particle and gelinite in the molten stream are filtered.Can adopt primary and secondary filter known in the polymer film manufacturing with the mesh size in the 1-30 micrometer range.Though point out that in the prior art such filtration is to the cleanliness factor of film and the importance of surface nature, the uniformity that its meaning also expands in the present invention.So each molten stream is sent to the gear pump of a continuous and uniform speed that is used for telomerized polymer stream by a neck tube.In order to guarantee molten uniformly stream temperature, the mixing arrangement of a static state can be placed on the end of neck tube, neck tube takes molten stream to the multilayer feeding device from gear pump, whole molten flow to end may be heated equably to guarantee having molten stream evenly to degenerate at the smelting process device minimum.

The multilayer feeding device is designed to two kinds or multiple polymer melts stream are divided into many layers, every layer of staggered these layer that inserts, and many layer fusions of two kinds or multiple polymers are single multilayer stream.Emitted from the molten circulation road of a master continuously from the layer of any given molten stream that part is molten to flow to the edge channel pipe, it provides a layer slit for respective layer in the feeding device arm.Have many designs, comprise that those are authorizing the 3rd, 737, No. 882, the 3rd, 884 of people such as Schrenk, No. 606 and the 3rd, 687, disclosed in No. 589 United States Patent (USP)s.Authorizing the 3rd, 195, No. 865, the 3rd of people such as Schrenk, 182, No. 965, the 3rd, 051, No. 452, the 3rd, 687, No. 589 and the 5th, 094, No. 788 United States Patent (USP)s and authorize the 5th of people such as Jewis, also described with the method for controlling laminar flow introducing layer thickness gradient in 389, No. 324 United States Patent (USP)s.In typical production technology, generally control laminar flow by the selection of in shape of processing each other edge channel pipe and layer slit and physical size, carrying out.

The edge channel pipe of two or more molten streams and layer slit are by desirable staggered like that, to form layer alternately.The arm that is used for multilayer heap layer feeding device downstream one side is made certain shape, with laterally compression and spread layer equably.The special thick-layer that is called protection border (PBL) can take out and send near branch pipe wall from any molten stream that is used for optical multilayer heap layer; perhaps send into by other feed streams, doing like this is in order to protect thin optical layers not to be subjected to the influence of wall tension and the unstability that may obtain flowing.

In optical application, want transmission or reflect the film of one or more special colors planning especially, in membrane plane, need the uniformity of point-device layer thickness.In practice, it is difficult will obtaining desirable layer uniformity according to this horizontal spread step.The quantity of required horizontal spread is bigger, and the heteropical possibility in the layer thickness profile that obtains is just bigger.Therefore, from the viewpoint of the uniformity of the layer thickness profile uniformity of film color (perhaps for), the layer slit of feeding device do relatively wealthyer being good.But the width that increases layer slit causes feeding device bigger, heavier and more expensive.Obviously, consider the optical homogeneity requirement of the film that obtains at last, the estimation of optimal layer slot width must be made respectively to each feeding device situation, and has used the reliable rheological data of the polymer of being considered and at the known polymer flow field simulation software of prior art Chinese character and the model of feeding device manufacturing cost.

Have in production in the film of special layer thickness or thickness gradient distribution (spreading all in the whole thickness of multilayer film, with prescriptive procedure it is being revised), Thickness Control is useful especially.For example, describe for certain several layer thicknesses design of infrared film, these design handles cause reducing to minimum in the higher hamonic wave of the color of the visible region of spectrum.The example of this film is included in RE3, those that describe in 034, No. 60 United States Patent (USP).

Another suitable film is included in the 5th, 360, the film of describing in No. 65 United States Patent (USP)s, this patent is described has six layers of alternately two component films of repetitive, and it has suppressed unwanted two, three in the visible wavelength range and quadravalence reflection between about 380-770nm and has reflected light in the infrared wavelength region between 770-2000n.

The design of another useful film is to describe being entitled as in the 09/006th, No. 118 U.S. Patent application of " multicomponent reflectance coating ".

As mentioned above, also available a kind of Mixed Design, the first of its multilayer heap layer is that design comes the light of reflection wavelength greater than about 1200nm, and has the AB repetitive and have the second portion of the alternating layer of equal optical thickness to be used for the infrared light of reflection wavelength between 770-1200nm substantially.A kind of like this combination of alternating layer causes across the light reflection of infrared wavelength region until 2000nm.

By design film or optical bodies in these constraintss, particularly when the infrared region of the single order zone of reflections at spectrum, at least can suppress the combination of some second orders, three rank and quadravalence higher order reflection along with the change of incidence angle, and the first harmonic reflection does not reduce in fact.This film and optical bodies are useful especially as infrared level crossing, and as the window film and not only requiring infrared protection but require good transparency and the similar application of light color in be benefit.

In the film each layer transmembrane preferably has different thickness.Usually be called layer thickness gradient.Select layer thickness gradient to obtain required reflection bandwidth.Common layer thickness gradient is linear, and wherein, the right thickness of thickest layer is than thick several percentage points of the right thickness of thin layer.For example, 1.055: 1 layer thickness gradient means that the thickest layer is to (adjacent with the facing surfaces of film) thick 5.5% than the thinnest layer to (adjacent with a first type surface).In another embodiment, layer thickness can be to reduce earlier from a first type surface of film to another face, increases then, and then reduces.It is believed that and do the belt edge that can provide steeper like this, thereby to transmission area a steeper or more unexpected transition is arranged from the echo area of spectrum.

To the method that obtain steep belt edge simply be described to the multilayer film that two kinds of optical materials " A " and " B " is arranged to alternate sequence.In other embodiments can three kinds or more kinds of different optical material.Every pair of layer with adjacent " A " and " B " constitutes an optical repeat unit (ORU), begin at the top of film with ORUI, and with the ORU6 end, the optical thickness of these ORU be OT1, OT2 ..., OT6.These optical thicknesses are the same with the term of determining in front " Dr ".At the design wavelength place, for the single order reflection (M=1 in equation I) of maximum, each ORU should have 50% f-ratio value with respect to A or B layer.Can think that the A layer has higher X-(in the plane) branch refractive index than B layer, this is because the former is thinner than the latter.Can divide ORU1-3 into a multilayer heap layer S1, wherein, the optical thickness of each ORU descends monotonously in negative z direction, and can divide another multilayer heap layer S2 into than ORU4-6, and wherein, the optical thickness of each ORU rises monotonously.Is helpful such as this thickness distribution producing aspect the steeper spectral transition.On the contrary, the thickness distribution of previously known film typically only rises or descends along a direction is dull.If some application needs can be included in the discontinuity in the optical thickness between these two the heap layers, to produce a simple recess shape transmission band spectrum.

Can design and improve transmission peaks and make even other thickness gradient of more precipitous belt edge (narrower transmission band).This can obtain like this, and in component heap layer, there, the part of heap layer has the thickness distribution of opposite curve each other arrangement layer, and the adjacent part of heap layer has slight curving form and is complementary with the curvature with the first of heap layer.The distribution of curve can be followed the functional form of arbitrary number; The main purpose of this form is to break the thickness repetition that appears at the strictness in the 1/4 ripple heap layer with being transferred to the layer that has only single wavelength.Additive function and SIN function that special function used herein is a linear distribution are to draw distribution with suitable negative or positive first order derivative.The second derivative of the thickness distribution that important feature is ORU is positive to redness (long wave) belt edge of reflective stack layer, and blueness (shortwave) belt edge of reflective stack layer is born.Noting, is the belt edge of a recess transmission band if involve, and then needs opposite consciousness.Other embodiment of same principle comprises that having a plurality of first derivative values is that the layer of zero point distributes.In all here situations, derivative relates to those derivatives by the optimum fit curve of the ORU distributions of optical thicknesses match of reality, and it can comprise the little statistical error of standard deviation sigma1 (σ 1) less than 10% optical thickness value.

Each original part (not comprising those PBL) of the multilayer heap layer that comes out from the feeding device conduit is commonly referred to as bag (packet).In the film of optical application, each bag is designed to make light reflection, transmission or polarization on a given wavelength band.Bag more than one can appear when multilayer heap leafing is driven feeding device.Therefore can design film on two or more being with, to provide optical property.These bands may be separate and have nothing in common with each other, maybe can be overlapping.A plurality of bags are constructed in the identical or different combination of enough two or more polymer of energy.By the gradient plate of structure feeding device like this and it, thereby be that all bag is reinforced, or come to feed in raw material, just can constitute a plurality of bags by two or more identical polymer for each wraps with the independent group of fusion sequence with a fusion sequence of every kind of polymer.Be designed to bag that non-optical properties (such as physical property) other gives film also can with optics package in single multilayer feeding device heap layer altogether.

Another method that forms double-contracting or many bags in feeding device is to form theirs from a feeding device bag by means of having the multiplier of multiplication factor greater than 1.Depend on the bandwidth and the multiplication factor of original packet, it is overlapping or separate a bandwidth gap between them that the bag that obtains at last can be formed in the bandwidth aspect.The people who knows this area knows that obviously for any given blooming target, best feeding device and multiplication war strategy depend on all multifactor, thereby must be determined on basis one by one.

Before multiplication, can add extra play to multilayer heap layer.These exterior layers are served as the role of PBL again, are specifically in multiplier.Behind multiplication and lamination, part PBL stream will form inner boundary between optical layers, and remaining then forms the top layer.Therefore, in this situation, bag is separated by PBL.In the end be fed to before the formation device, can add additional PBL, and finish extra multiplication step such as mould.This reinforced before, though multiplication whether finish, no matter and whether PBL added (if the words that have) before described multiplication, can be added to last extra play the outside of multilayer heap layer.These will form last top layer, and the exterior portion of the PBL that had before applied will form time top layer (sub-skin) below these last top layers.Mould is carried out the additional compression and the width spread of molten stream.Produce uniformity when in addition, the proper blank of mould (inner conduit and the pressure area that for example, comprise it) design being left mould across the layer distribution of blank.

Be subjected to the influence of wall stress and the unstability of the possible molten stream that causes thus though often the top layer is added to multilayer heap layer to prevent thin optical layers, the reason that other also can be arranged is at thick-layer of the surface of film interpolation.Concerning those were familiar with the people of film coextrusion processes, it was significantly that many things are arranged, but and these comprise such as adhesion strength spreadability, release, coefficient of friction, also have for example barrier nature, against weather, the anti-wiping and abrasion strength.Except that these, surprisingly, at film by single shaft continuously or biaxial stretch-formed very unequally when long, by means of select a kind of top layer polymer (it with subsurface or the most close optical layers polymer is all bonding must be fine, and when stretching, it is difficult for orientation voluntarily), the tendency that can suppress " cracking " substantially or tear easily or rupture along the higher direction of extensibility.The situation of example be on the optical multilayer of the homogeneous polymers that comprises PEN heap, use PEN copolymer (coPEN) as the top layer, it has the comonomer composition, is enough to restrain degree of crystallinity and/or crystalline orientation.Make comparisons to the similar film that does not have the coPEN top layer, when, in such structure, having been observed significant cracking and suppressed when not stretching or stretching slightly by high elongation on the direction of film on a plane perpendicular to this in-plane.The people who is familiar with this area can select similar top layer polymer to replenish other optical layers polymer and/or inferior top layer polymer.

At feeding device with in subsequently for the molten stream that guides in the casting of mould casting port position, temperature control is of crucial importance.Although temperature homogeneity is usually desirable, in some cases, the pre-prepared thermograde in feeding device or in feed streams, be used for making cell thickness to distribute contracting narrow or broadening up to about 40 ℃ of thermal gradient energies.The feed streams that enters in PBL or the surperficial piece also can be set at the temperature different with the mean temperature of feeding device.These PBL or surfactant fluid are set to often and exceed 40 ℃ reducing viscosity or elasticity in these protectiveness stream, thereby have strengthened the validity as protective layer.Sometimes, these streams may reduce on temperature and reach 40 ℃, to improve the rheology coupling between the remainder of they and fluid.For example, reduce the temperature of hanging down the viscosity top layer and can increase viscosity coupling and enhance fluid stability.Other the time, buoyancy effect need the coupling.

Observe shear rate and influence viscosity and other such as the flexible rheological equationm of state.With the coupling of viscosity (or other rheology effect) for the relative shape of the shear rate curve of coextrusion polymer, the improvement of showing fluid stability sometimes.In other words, minimizing of maximum mismatch may be a suitable target of convection cell stability between such curve.Therefore, in molten stream, can help the difference of in the whole stroke of molten stream balanced shearing or other flow rate in each different phase temperature difference.

Blank is cast on the chilling roll.This roll is also referred to as casting wheel or casting ladle sometimes.Preferably assist casting by the static pinning, its details are known in the production technology of polyester film.To multi-layer optical film of the present invention, when being set, the parameter of static pinning equipment should carefully carry out.Varied in thickness along the periodic casting blank of extruding direction of film often is referred to as " pinning vibration " (pinning chatter), and it must be avoided as far as possible.Known adjusting electric current, voltage, pinning metal wire thickness and pinning metal wire have an effect with respect to the position of mould and casting chilling roll, must set about setting on the basis of situation one by one by the people who is familiar with this area.

Because on one side wheel contact and at another side is the air contact, so blank may have surface texture edge (sideness), degree of crystallinity or other character is arranged.This may be to want and be undesired in other is used in some application.When wanting this edge difference minimized, sting and send roll and the combination of chilling roll for available one, on one side strengthen cooling off or to not so can being that the cast air of blank provides smooth.

In some cases importantly, while multilayer heap layer be to select on chilling roll limit, obtaining splendid cooling.For example, often require the thinnest layer is placed on the most close chilling roll place by multilayer that layer thickness profile constitutes heap layer.

In some cases, require to provide rough surface or superficial makings to improve the processing in coiling and/or conversion subsequently and utilization to film.Many this examples are for being familiar with known to the people of film manufacturing process.When attempt this film is used when contacting with a glass plate or second layer film close, the example that special and a blooming of the present invention have close relation occurred.In these cases, blooming selectively " is drenching " phenomenon that can cause being referred to as " Newton's ring " on the flat board or on second tunic, and it damages optical homogeneity on a large scale.A veined or coarse surface prevents to drench the required contact compactness and the appearance of Newton's ring.

As everyone knows, in the technology of polyester film, comprise very a spot of fine particle material, often it is called " antiseize paste " (slip agent), this rough surface or texture are provided.This can accomplish in blooming of the present invention.But, introduce the light transmission how much a spot of smog has reduced film thereby comprise the antiseize paste particulate.According to the present invention,, then under the situation of not introducing smog, also can even more Newton's ring can be prevented effectively if when film is cast, contact so that rough surface or texture to be provided with the protruding roll of nick.The protruding roll of nick is preferably stung as one casting wheel and is sent roll to use.Change a kind of way, casting wheel itself may form microtexture so that a similar effect to be provided.In addition, have the casting wheel of microtexture and have stinging of microtexture and send roll to use together, provide nick protruding two-sided coarse or texture.

In addition, the present inventor is surprised to find, and send roll in smooth the stinging that casting chilling roll place uses, on one side except as discussed above can help air for film cools off, can also significantly reduce the size of mould line, pinning vibration and other thickness rise and fall.May stride across blank it is poured into uniform thickness, or control of forming sotck thinkness with the mould sprue gate and preplan good distribution.This distribution may improve uniformity when membrane process finishes.In other situation, a uniform casting thickness provides best uniformity when membrane process finishes.The control vibration is important to reduce " vibration " when casting the multilayer blank in process equipment.

Even under a fixing shear rate, also may be important in each holdup time in operation stage.For example, by regulate that the holdup time can change or key-course between the phase counterdiffusion.The phase counterdiffusion here is meant in all mixing of storeroom of respective layer and the process of reaction, for example, comprises the various molecular motions such as diffuse normal, cross-linking reaction or ester exchange reaction etc.Phase counterdiffusion is fully wished, to guarantee the bonding of good interlayer and to prevent layering.But too much mutual diffusion energy causes such as harmful effects such as composition difference of significantly losing interlayer.The phase counterdiffusion also may cause copolyreaction or mixing at interlayer, and this may can reduce the alignment capability of layer when stretching.Therefore the scale of holdup time that this harmful phase counterdiffusion takes place, can make the holdup time optimization usually than obtaining good ply adhesion required much bigger (for example, the size of an order of magnitude).But some may be useful when being diffused in the distribution (for example making the structure of wrinkle) that forms the interlayer component on a large scale mutually.

The effect of phase counterdiffusion also can change with further layer compression.Therefore, this effect under given holdup time also be that time at interval in respect to the function of the layer compression state of last layer compression ratio.Because thin layer is more responsive to the phase counterdiffusion, generally they are placed on the most close casting wheel place so cool off for maximum.

At last, the present inventor is surprised to find that after casting, cooling and stretch multi-layer, by heat-setting at high temperature, diffusion energy is reinforced mutually.

The condition at casting wheel place is provided with according to desired result, and when hope during by optical clarity, chilling temperature must be enough cold with restriction smog.For polyester, typical cast temperature scope is between 10 ℃ and 60 ℃.The higher part of this scope can with the use that connects together of level and smooth or concavo-convex roll, then cause more effective cooling than lower part for the thick stock material.The speed of casting wheel also can be used to control cooling and layer thickness.For example, the pump rate that can slow down extruder is cut with reduction should rate or increase the phase counterdiffusion, and the speed that increases casting wheel is to keep the thickness of desirable casting blank.Thereby the thickness of casting blank is chosen such that when the end that all stretches has incident reduced down in thickness, the topped desirable band of last layer thickness profile.

The stretched multi-layer blank is to produce last multi-layer optical film.A main reason that stretches is to be used in the optical power that the birefringence that produces in one or more material layer increases last optical stack layer.Typically, at least a material becomes birefringence under stretching.This birefringence is caused by material molecular orientation under selected stretching process.This birefringence often greatly increases (for example, stress cause crystallization) with the coring that is caused by stress in the stretching process or strain and crystal growth.Degree of crystallinity has suppressed to present birefringent molecular relaxation, and crystal itself may be also directed with stretching.Sometimes, some all crystal may be pre-existing in or before stretching by the casting or preheating cause.Other reason of blooming of stretching may include, but is not limited to increase output and improve engineering properties in the film.

In a typical method of making the multilayer optical polarizer, used single stretching step.This operation may be finished in stenter or length adjustment machine (orienter).Though some stenter is furnished with fully on the blank path or operating direction (MD) stretches dimensionally or the mechanical device of loose (contraction) film, typical stenter and blank path lateral ground (TD) stretch.Therefore, in this typical method, film is to be stretched along the direction in the plane.Second plane inside dimension is not to keep constant exactly as be necked to a width smaller the length adjustment instrument as in a stenter commonly used.This constriction may be important and increase with extensibility.For a flexible incompressible blank, its last width can be estimated as theoretically along its length that the subduplicate inverse of extensibility multiply by the width of beginning.In this theoretical situation, its thickness also reduces with this same ratio.In practice, this constriction may produce and be slightly wider than molded breadth, and the thickness of blank may descend to keep volume conservation approx in this case.But, because the unessential conservation of volume, so deviation is possible from this is described.

In the typical method of making the multilayer minute surface, birefringent material all is orientated along the direction in the plane with two step stretching process.Arbitrary combination of the stretching process single step operation that to be the permission narrated stretch along the both direction in the plane.In addition, can be the stenter that stretches along operating direction (MD) with allowing, for example can be one after the other or the biaxial stenter that side by side stretches along both direction.In this a kind of situation in back, may use single biaxial stretch-formed operation.

In also having a kind of method of making multilayer polarizer, adopted repeatedly stretching process, it has utilized the different performance of various materials to each other stretching step, in single coextruded multilayer membrane process the different layers that contains different materials is carried out in various degree orientation each other with type.The also available the method for mirror forms.This blooming and operation have further narration being entitled as in the 09/006th, No. 455 U.S. Patent application of " blooming and manufacture process thereof ".

In another embodiment of blooming, can make polarizer by a twin shaft operation.In also having an embodiment, the mirror of balance can be made with an operation, this operation has produced two kinds or the multiple material that significant birefringence (thereby in the plane asymmetric) is planar arranged, make asymmetric coupling to form a balance result, for example, all have near the refractive index difference that equates along two main directions in the plane.

In some operation, owing to comprise that the influence of the process conditions of blank under the tension change can produce these rotation.Sometimes be referred to as in this film production on common stenter " forward arc " (bowforward) or " backward arc " (bowbck).In order to improve output and performance, the even directionality of optical axis is to wish usually.Can use the operation of restriction this bending or rotation, such as controlling by means of method machinery or heat or isolating tension force.

Observe frequently that the cross directional stretch film along operating direction is uneven in stretching-machine, when near the edge that is being clamped of blank, thickness, direction or both become.Typically, the temperature evil ways hypothesis that these variations are with the blank temperature at the close edge that is clamped is lower than in blank central authorities conforms to.This heteropical result makes the available width of film in completion seriously reduce.This restriction is to blooming of the present invention even more severe, because tiny difference can cause striding across the inhomogeneities of the optical property of blank in film thickness.As by the present inventor recognized, stretching, thickness and color homogeneity can improve the extra heating in edge near the film blank of tenter clip gap with infrared heater.This infrared heater can be used in before the preheating zone of stenter, in the preheating zone, in drawing zone or in combination place of these positions.The people who is familiar with this area will understand the subregion that increases infrared heat and many selections of control.And the combined possibility of variation that heating of infrared edge and casting blank is striden across the sotck thinkness distribution also is conspicuous.

For some multi-layer optical film of the present invention, crucial is, stretched film like this, thus have identical value in one or more character that the film of completion is measured along machine direction and horizontal direction.This film often is referred to as " balance " film.Machine direction and horizontal direction balance obtain by the choice of technology process conditions of knowing in the Biaxially oriented film manufacturing technology.Typically, the technological parameter of detection comprise machine direction orientation preheat temperature, exhibition temperature and draw ratio, the stenter preheat temperature that stretch and also relate to the stretching of stenter sometimes after the parameter in zone.Other parameter also may be important.Typically, the experiment of finishing and analyze design is to draw the appropriate condition combination, and the people who is familiar with this area will understand, and need severally various membrane structures and every film production line of producing film to be estimated.

Similarly, can be influenced by various process conditions such as contraction when the rising temperature and the reversible such dimensional stability parameter of thermal coefficient of expansion, similar to the situation of the film of the routine that is known in the art.These parameters include, but is not limited to heat curing temperature, heat cure duration, when heat cure horizontal direction size relaxation " toe inwardly " (toe-in), blank cooling, blank tension force and around the heat behind roll " insulation " (or annealing).Also have, the people who is familiar with this area can finish the experiment of design, requires to determine optimum condition with the given dimensional stability of a cover that a kind of given film that moves on a given film production line is formed.

For forming, should make an appraisal to the conforming needs of careful control and process conditions according to high-quality blooming of the present invention.Temperature is very big to the inhomogeneity influence that stretches, and therefore uniform film is usually wished to have even temperature.Equally, also wish to have the thickness of film and the uniformity of component.The preferable inhomogeneity method that can obtain is smooth uniform films of casting, stretches it then equably to make last film uniformly.Usually, last film character can more even (for example, the color of deflecting angle) and better (for example, interlayer is bonding) under this technology.In some cases, casting thickness distributes and can be used to compensate unbalanced stretching to produce the caudacoria of uniform films thickness.In addition, infrared edge heating discussed above can with the casting thickness use that connects together that distributes.

C2. look uniformity

As what in this joint of background of invention, point out, can make optics according to multilayer film of the present invention and other, thereby the film considerably beyond prior art in a very big scope, showing of can reaching physics with uniformity optics.The method according to this invention, the distortion of the thickness that runs in former casting (the be not stretch) film and the distortion of optical thickness are to be used in biaxial stretch-formed this casting blank of multiplying power between about 2 * 2 and about 6 * 6 (about 4 * 4 better) to avoid, it has the trend of the variation that makes transverse layers thickness, so make change color, but be not sudden change.And, because film is to be made by the casting blank (film of a completion of direct pouring is opposite with not stretching) that stretches, because it is significantly less to occur the spread of layer in narrower mould, so desired narrower casting blank allows the layer thickness profile in extruding mould that less distortion can be arranged.

Many other technologies that discuss in several in the above joints and that want to improve layer thickness homogeneity are considered, because color is directly relevant with layer thickness, so also improved color homogeneity.These rheology coupling, filtration, feeding device design, multiplier design, mould design, edge protection interlayer (PBL) and top layer selection, temperature control, static pinning (pinning) parameter, sotck thinknesses that include, but is not limited to multi-layer resinous system change the use of scanning means.Casting the nip use, vibration control of cylinder (niproll) and the heating at blank edge in stenter.

In the design of extrusion equipment and processing and the error of extruding in the control all will cause system and error at random.In general, to even color film, this random error can cause color upper edge blank and stride across the variation of blank; And systematic error, though can not change, will be influential with the change color that strides across blank to total color of film.

Also have each other layer at random and error system all can occur to whole film thicknesses.By light transmission or reflectance spectrum, the easiest detection and monitor total film thickness error.Therefore, an online spectrophotometer can be set, when film is measured its spectral transmission when line leaves, thereby provide essential information to measure color homogeneity and provide feedback for technology controlling and process.The error of respective layer may influence or not influence the color of finding out, the place that mainly depends on their places in the optical stack layer also depends on the size of error.

Systematic error is a deviation repeatably, and it is from the design thickness of layer any or all of in the heap layer.They be because approximate in the intrinsic design of the polymer flow model that is used for designing multiplier and feeding device, or because the mismachining tolerance in feeding device and mould.These errors can enoughly design and reprocess and eliminate again, drop to design standard until these errors.These errors also can reduce with feeding device of processing, and it does not have the help of multiplier just can produce the number of plies required in the blooming.

Random error can be by the temperature change in change in the feeding device and the mould district; The resin inhomogeneities; By the inappropriate control of fusion sequence to melt temperature, this fusion sequence makes some part deteriorations of melt-flow selectively; Feeding device or mould are because the pollution that deterioration or the resin that burns cause; Cause such as technology controlling and process errors such as the variation of melt-flow pressure, temperature and pumping rate and the unstability of hydrodynamic flow etc.In order to avoid causing the condition of this flow instability, the model of stream should provide input to feeding device and mould design.

Total thickness evenness is subjected to the influence of speed fluctuation, system vibration, mould clearance control, static pinning and the film stretching condition of mould design, casting wheel.These variations can be at random or system.Systematic error needn't provide constant (for example, constant) color.For example, the vibrational energy of mould or casting wheel causes the magnitude of one-period to change at 0.5 spatial color that arrives the repetition of 50cm.In application such as decorating film etc., wish in the film of completion, to have the spatial color of one-period to change, can intentionally give casting wheel to controlled vibration.But in hope color homogeneity and good THICKNESS CONTROL being arranged is necessary place, and this casting wheel and a direct CD-ROM drive motor (for example, gearless is slowed down) cooperate.An example of this motor is a direct current brush servo motor, such as can being the motor of TT-10051A from portion's product number that Kollmorgan buys.Can use the high-speed motor that has gear reduction, but must be high-quality system with special-purpose electric tuning and smooth gear-box.System vibration, especially mould can be by reducing to minimum with respect to the vibration of casting wheel on the cement platform on the ground that casting bed is placed on casting equipment.Dashing other method slow or that isolate will be conspicuous for the people who is familiar with mechanical technology.

Vibration source can change scanning means by means of a sotck thinkness and recognize.If can be from cycle of oscillation of a kind of like this output of device identification, then can be to the operation key element, so that the external source of the oscillation behavior that demonstrates same period done a search.So these unit can make more solidly with method well known in the prior art, vibrate damped or vibration and mould and casting wheel are isolated, if or unessential to operation, just simply disconnect or settle again.Therefore, because the periodicity of the rotation of extruder screw and the vibration recognized can be isolated, for example, between extruder gateway and neck tube, use a kind of damping material, and the vibration that is identified owing to the periodicity of room fan can be removed by turning off or reapposing this desk fan.In addition, can mould and casting bed mechanically be coupled together by the form of some firm superstructure, prevent to cause the relative motion of the vibration between mould and casting bed for the vibration of mould that can not be eliminated fully or casting bed.To a kind of like this many designs of vibrating the mechanical connection of intercommunication will be conspicuous.In addition, when in film, using strain-hardening material, then stretch and to carry out in enough low temperature, stride across the even stretching of blank with generation, and the pinning metal wire should firmly be laid by the jail.

The casting wheel driving mechanism that has a constant velocity of rotation precision by use has obtained the additional control to layer thickness or optical thickness.Casting wheel is designed to vibrationlessly also operate under friction, otherwise can causes sotck thinkness " vibration ", and cause the layer thickness variation of following blank direction subsequently.The applicant has had been found that those vibrations of the relative motion that is created between mould and the casting wheel, when extrudate causes effective velocity variations casting wheel when mould pulls out.These velocity variations cause the modulation in film thickness and optical layer thickness, and this is particularly remarkable for the strain-hardening material that uses valuably in making blooming of the present invention.Therefore, there is not these control, in blooming of the present invention, is enough to remarkably cut down the look uniformity extruding the normal vibration that operation runs at casting wheel.The product of the colour shifting film that method of the present invention can have been made with polymeric material for the first time, the look that has height under any one special visual angle is even.Therefore, can make film by method of the present invention, wherein, desirable a special incidence angle the light transmission or reflection bandwidth at least at 10cm ²Area on change less than about 1 to 2nm, and be more preferably 100cm at least ², and wavelength value ripple wavelength change on area identical of the belt edge edge of its spectral reflectance peak value be less than approximately+/-4nm.

Illustrate that by several examples these examples are done a comparison to the film of film of the present invention and prior art with the possibility of method of the present invention in improvement aspect the look uniformity.

Example C2-1

Following Example has illustrated the look uniformity of the several common color films that can buy on market.

Obtain the sample of a kind of blooming that on market, can buy (8631 red/green) from Mearl company.This film is (for example, when the visual angle changed, the adjacent region on film was changed into the dissimilar color of irregular shape, thereby gave one of this film appearance of " oil on the water ") that halation is arranged in appearance.Color profile in the film scope give it one similar in appearance to wood grain (woodgrain) appearance with the topographic map of a color-coded hilly country.

The transmitted spectrum of film is taken from visible wavelength with " Instaspec " diode array of Oriel.Though, when other angle of incident, also observed similar spectrum, each of these spectrum is taken from vertical incidence.It is 0.5 inch place that these spectrum are taken from striding across blank direction spacing, place's beginning when an end 0.5 of membrane sample.Suppose the small-sized of it, but sample itself is likely and downcuts from the blank of big material.Because each in these spectrum shows that to one desirable look uniformity is identical, so the variation of spectrum is a symbol of look even variation.

The Mearl film is shown in Figure 32 and 33 at the spectrum at these each some places, corresponding respectively blank down and the direction that strides across blank.As what see in these figure, the Mearl film demonstrates substantial variation striding across on the look uniformity on the direction of blank, on the distance of 76.2mm (3 inches), amount to+/-13nm.Spectrum change in following blank direction is smaller, but still is attractive.

Example C2-2

The following blank and the spectrum change that strides across blank of the green transmission film among the routine E1-2 have been detected.The spectrum that strides across blank is got at a distance of 1 inch and has been got several inches, in the blue ribbon edge of the passband that is centered close to 550nm place edge, only show+/-4nm mobile.The spectrum that the spectrum that strides across blank is shown in Figure 34 and following blank is shown in Figure 35.

Example C2-3

Also analyzed the uniformity of the blue transmission film of routine E1-1.A series of curves of spectrum are at following blank and stride across blank and obtain at a distance of 0.5 inch place.Both local uniform are identical for the yardstick that is shown in Figure 36 (this figure makes following blank direction) substantially.

The film of example C2-2 and C2-3 seems very even on color, do not see the distinguishable variation that goes out in 1 to 2 inch the district adjacent leaving.So, on film 1 to 2 square inch area partly, when sample during in various angular turn color change simultaneously.Similarly, when the film of routine C2-2 or C2-3 is curved s shape, and on all angles, watch the color belt that is produced as the steep border that straight line is arranged.

The spectrum change of film has obtained reaction in the color appearance of film.It is that the color of the magnitude of 12.7mm (0.5 inch) is (though because from point to points in difference of spectral shape still some spot) quite uniformly about diameter that the Mearl film comprises area, but the look uniformity in film, on bigger area, worsen, on about 1 square inch area, demonstrate the following variation of blank on the belt edge edge to be about+/-7nm.On the contrary, the film among the routine C2-3, demonstrates on the blue ribbon edge down on the length of blank at 63.5mm (2.5 inches)+/-variation of 3nm, and the green film among the routine C2-2 is on 3.5 inches following blank distance, demonstrates on green belt edge+/-variation of 4nm.

As what see from top spectrum, the film that the method according to this invention is made demonstrates optical thickness in fact uniformly on a sizable membrane area.Thus, when with physics with the optical thickness uniformity be the lower film of degree when comparing, cause as the more precipitous of function of viewing angle and color transition faster.

C3. the change color in cycle

Though the look uniformity is important in many application of film of the present invention, in other is used, as decorative film, look uniformity or unessential or undesirable.In using, those wish coloured variation.They may intentionally be crossed or the varied in thickness of the desired space frequency that causes along the part handle of blank is applied on the film of the present invention at any point before blank cooling, cause the modulation of optical stack layer thickness in such a way.Though have a lot of methods to finish (for example, be used in cause vibration in the casting wheel),, can apply this modulation easily by in pinning wire, causing the vibration an of frequency of wanting (or several frequency).For example, by causing vibration pinning on the wire, the color of polarizer film is being changed from achromatic grey transmitted colour to redness periodically crossing on the straight line of film.This red streak is separated by 6 millimeters in following blank direction.The calculated rate that pins the wire vibration is 21Hz.

The also available extruded film of the present invention of local random change color obtains, and it has the decorative effect that inner minute bubbles are attracted into generation.Bubble can produce with several different methods, comprise not resin be dried to fully that people often do like that or with overheated slightly the resin of heat-sensing (such as PMMA), produce same effect.These local minute bubbles that form distort microbedding (microlayer) and have caused local change color, and it can provide the outward appearance of level (depth) in certain several example.

Though the method for narrating above to causing change color likes well at a kind of non-homogeneous film of instruction, initial Ranvier's membrane (it has high stopband reflectivity and high colour saturation) with even color, though, be satisfied aspect average tone, colour saturation and the brightness of this decorating film of control by a known method local failure.The local color here said changes, and is then more noticeable when it is used to a uniform colour shifting film of the belt edge that has the zone of reflections of intrinsic high reflectance and have high slope.

As noted above, the variation of the film middle level thickness that the vibration in casting wheel causes casting rate to come and go to cause.The frequency of this vibration (or several frequency) can modulatedly apply the repetitive sequence or the pattern of color and give last film.In addition, these change in color can be finished in the typicalness of the color transition characteristic of not damaging film of the present invention, thus allow color in the abundant film product of this color (topped whole visible spectrum usually) seem flicker or when incidence angle be mobile when changing.

The also available template of the change color in cycle (pattern) is molded on the film.Since the finished part of this mold pressing no longer with this fact of remainder coplane of film, so it demonstrates one or more different colors than the remainder of film.Therefore, for example use a fishnet figure (for example, the gold on red background) or a sign to come mold pressing colour shifting film of the present invention, produced surprising effect.

In some example, similar principle can be used for removing or transferring the color transition in the cycle in film, thereby improves the color homogeneity of film.Therefore, find a source, the vibration of a given frequency or a period demand frequency is put on blank, then same-amplitude (still, the position mutually opposite) vibration can be applied to this blank (for example, passing through casting wheel), thereby cause destructive interference from this operation, to remove this source effectively.

C4. obtain the method for polarizer refractive index coupling/mismatch

Choosing is used for the material of colour shifting film of the present invention and the degree of orientation of these materials, is preferably selected, thereby have an axle at least in the layer of the polarizer that completes, and refractive index associated therewith equates substantially.The coupling of the refractive index related with this, the horizontal axle of direction that general (but being not essential) is and is orientated causes there is not reverberation haply in that plane of polarization.

Typically, colour shifting film of the present invention is to make with the alternating layer of at least the first and second kinds of polymeric materials.Wherein, first kind of material has higher birefringence than second kind of material.Usually be that second kind of material is chosen as isotropic.But second kind of material also may be negative bireflectance, and in other words, the refractive index that it is associated with differently-oriented directivity after stretching presents minimizing.If the birefringence of first kind of material is positive, the birefringence that the negative strain of second kind of material causes just help being increased in axis of orientation be associated in abutting connection with the difference between the refractive index of (adjoining phase) mutually, and still be negligible perpendicular to the reflection of light of the plane of polarization of differently-oriented directivity.Should in expection will have most of zone of spectrum of color transition effect, be less than 0.05 approximately after the orientation at the refractive index difference between mutually that is orthogonal to differently-oriented directivity, be less than approximately 0.02 preferable.

Second kind of material also may show the birefringence that positive strain causes.But this may change with heat treatment method, with the refractive index of coupling perpendicular to the axle of the differently-oriented directivity of continuous phase (continuous phase).Heat treated temperature should be too not high, in order to avoid weaken the birefringence in first kind of material.

Under various environment (for example, special extensibility and temperature) coupling/mismatch of being wanted of influencing on refractive index with stretched film or optical bodies also is possible, wherein, special layers in the film will be orientated (change of refractive that causes them) selectively, but the refractive index of other layer in the film is unaffected substantially.In multilayer film, selectively the method for some layers orientation is narrated being entitled as in the 09/006th, No. 455 U.S. Patent application of " blooming and manufacturing process thereof ".If want, can enough this methods in the specific layer of film, obtain real uniaxial orientation.

D. material is selected

Explained and be applicable to that various polymeric material of the present invention is used to make the multi-layer optical film of coextrusion.For example, United States Patent (USP) 4,937,134; 5,103,337; 5,1225,448,404; 5,540,978 and 5,568,316 (people such as Schrenk) and 5,122,905; Listed and the described polymeric material of 5,122,906 and 5,126,880 (Wheatcey and Schrenk) is applicable to makes multi-layer optical film of the present invention.Wherein interested especially is United States Patent (USP) 5 for example, 486,949 and 5,612,820 (people such as Schrenk), United States Patent (USP) the 5th, 882,774 (people such as Jonza) and be entitled as U.S. Patent application 09/006, the 601 described birefringent polymer of " the copolymerization polyester of modification and improved laminated reflective film ".For the preferred material of preparation film, should satisfy several conditions to make multi-layer optical film of the present invention.At first, these materials should be made by two kinds of different polymer at least, and number is not limit, and three kinds or more kinds of polymer are useful in concrete film.Secondly, the stress optical coefficient of at least a (being called " first kind of polymer ") better has bigger absolute value in two kinds of required polymer.In other words, when stretching, better can form bigger birefringence.According to purposes, can two orthogonal directions in membrane plane between form dielectric grid, direction and in one or more planes perpendicular to form dielectric grid between the membrane plane direction, or in the combination of these directions form dielectric grid.Have under this special situation of very big independence (widelyseparate) at isotropic refractive index,, can reduce requirement the birefringence of first kind of polymer though that birefringence remains usually is desirable.This special case takes place in the time of may forming level crossing film and polarizer film at selective polymer so that with biaxial stretch-formed method (planar two vertical direction stretched film).The three, the first kind of polymer should can keep birefringence after stretching, thereby makes the film of making at last have the desired optical property of wanting.The 4th, another kind of required polymer (being called " second kind of polymer ") should be selected like this, makes that promptly it obviously is different from the refractive index of first kind of polymer in this direction in the refractive index of a direction at least in the film of in the end making.Because polymeric material generally is chromatic dispersion, refractive index is different with wavelength in other words, so these conditions must be paid attention to according to interested peculiar spectrum bandwidth.

The others that polymer is selected depend on concrete purposes.For polarizing coating, first kind of polymer is obviously different in the refractive index of a membrane plane direction with second kind of polymer in telolemma, simultaneously with the membrane plane of this direction quadrature in refractive index difference to be reduced to minimum be useful.When first kind of polymer has bigger refractive index during in isotropism, and has positive birefringence (in other words, its refractive index increases with draw direction) time, then second kind of polymer generally will be selected for use after stretching and have the refractive index of coupling and have alap refractive index at draw direction at the in-plane that is orthogonal to draw direction.On the contrary, when first kind of polymer has little refractive index during in isotropism, and when having negative birefringence, then second kind of polymer generally will be selected the refractive index that has coupling after stretching at the in-plane that is orthogonal to draw direction for use, and high as far as possible in the refractive index of draw direction.

In other words, can select first kind of polymer, when isotropism, it has positive birefringence and has medium or low refractive index, and perhaps when isotropism, it has negative birefringence and has medium or high refractive index.In these situations, second kind of polymer generally can be selected like this, and promptly its refractive index will or mated with draw direction plane orthogonal direction and first kind of polymer phase at draw direction after stretching.In addition, second kind of polymer generally can be selected like this, promptly makes refringence maximum at remaining in-plane, and no matter this is by making that direction have very low refractive index or having very high refractive index finishes.

A kind of planar index that makes is a film of selecting first kind of polymer (it can form tangible birefringence when stretching) and second kind of polymer (it seldom form during in stretching or not form dielectric grid) also only finally to obtain an in-plane stretching in direction coupling and in the method for orthogonal direction mismatch.Perhaps, the optional self energy of second kind of polymer forms opposite with first kind of material (bearing-positive birefringence or just-negative birefringence) birefringence.Another kind method is to select first kind of polymer and second kind of polymer, and they can both form dielectric grid when stretching, but stretches it along two orthogonal directions; Select stretching condition (as relaxation after temperature, draw ratio, the stretching etc.).Described method causes first kind of polymer and/or second kind of polymer to have unequal degree of orientation along two draw directions, make refractive index approximate match, refractive index and the interior obvious mismatch of refractive index of the face of the quadrature of first kind of polymer in the plane orthogonal simultaneously in the face of refractive index and first kind of polymer in the plane of second kind of polymer.For example, can select stretching condition, have the characteristic of biaxial orientation in the film that kind of the polymer of winning is in the end obtained, mainly be the characteristic of uniaxial orientation and have in the film that second kind of polymer in the end obtains.

Noted earlier only is exemplary, can be understood as these technology and other technical combinations to be got up be used to obtain polarizing coating so that in a plane direction refractive index mismatch, and mate relatively in plane orthogonal direction refractive index.

Have different considerations for reflection or level crossing film.As long as film does not have polarization property concurrently, then any direction refractive index in the membrane plane has same standard.So for arbitrarily given, the direction refractive index normally equates in plane orthogonal or approximately equal.But, big as far as possible to the difference of the membrane plane refractive index of the membrane plane refractive index of first kind of polymer and second kind of polymer.Therefore, if first kind of polymer has high refractive index when isotropism, then it better also has positive birefringence.Equally, if first kind of polymer has low refractive index when isotropism, then it better also has negative birefringence.Second kind of polymer seldom forms or form dielectric grid not when stretching, or form dielectric grid (just-negative birefringence or negative-positive birefringence) is good on opposite meaning, thereby make the membrane plane refractive index of second kind of polymer in the film that in the end obtains and the membrane plane refractive index of first kind of polymer differ big as far as possible.If the level crossing film also has certain polarization property concurrently, these standards and the standard of listing above to polarizing coating suitably can be combined so.

Can be the special case of Coloured film as level crossing and polarizing coating.Therefore, be suitable for the identical standard of summarizing above.The color of seeing is result reflection or polarization of one or more concrete bandwidth of spectrum.The bandwidth that multilayer film of the present invention works is determined by the thickness distribution that is used for the optical stack layer.But, also necessary wavelength relationship or the dispersivity of considering the refractive index of first kind of polymer and second kind of polymer.Can understand infrared and ultraviolet wavelength are suitable for and the same rule of visible light colors.

Absorbance is another Consideration, and to most application, in the interested bandwidth of described film, it is useful that first kind of polymer and second kind of polymer all do not have absorption band.Therefore, all incident lights are not that reflection is exactly transmission within described bandwidth.But, some to be used, it is useful that one or both in first and second kinds of polymer all or partially absorb special wavelength.

Though many polymer can be selected as first kind of polymer, some polyester has especially big birefringence.Wherein gather 2,6-(ethylene naphthalate) (PEN) often is selected as first kind of polymer of film of the present invention, it has very big positive stress optical coefficient, after stretching, can effectively keep birefringence, and in visible-range, seldom or not absorb, it has big refractive index in isotropic state.When the plane of polarization is parallel to draw direction, its refractive index of polarized incident light of 550nm wavelength is increased to up to about 1.9 from about 1.64.Its birefringenct property increases by its molecularly oriented of increase, and described molecularly oriented can increase by being stretched to a bigger draw ratio when other stretching condition is constant.

Other hemicrystalline poly-naphthalate also is suitable for as first kind of polymer.Gather 2,6-naphthalenedicarboxylic acid butanediol ester (PBN) is exactly an example.These polymer can be homopolymers or copolymer, as long as the comonomer that uses does not significantly damage stress optical coefficient or the retention of the back birefringence that stretches.Term " PEN " can be regarded as and comprises the PEN copolymer that meets these restrictions in this article.In practice, these restrictions have applied a upper limit to the content (content) of comonomer.The exact amount of comonomer will change with the difference of employed one or more comonomers.But, can improve other performance if add comonomer, then can take into account these performances.These performances comprise, but are not limited to, improved viscosity, and lower fusing point (causing lower extrusion temperature) is with rheological characteristic coupling and the favourable migration that makes the stretch process window owing to the change of vitrification point preferably of other polymer in the film.

Be used for gathering 2, the 6-(ethylene naphthalate) gathers 2, and the suitable comonomer of 6-naphthalenedicarboxylic acid butanediol ester etc. can be dihydroxylic alcohols or two former carboxylic acids or its ester.The dicarboxylic acids comonomer comprises, but is not limited to terephthalic acid (TPA); M-phthalic acid; Phthalic acid; All isomeries of naphthalenedicarboxylic acid (2,6-, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-2,4-, 2,5-, 2,7-and 2,8-); Diphenic acid, as 4,4 '-diphenyl dicarboxylic acid and isomers thereof, trans 4,4 '-Stilbene dicarboxylic acids and isomers thereof, 4,4 '-diphenyl ether dicarboxylic acids and isomeric compound thereof, 4,4 '-diphenyl sulphone (DPS) dicarboxylic acids and isomers thereof, 4,4 '-benzophenone dicarboxylic acids and isomeric compound thereof; The halogenated aromatic dicarboxylic acids, as 2-chlorine terephthalic acid (TPA) and 2, the 5-dichloroterephthalicacid acid; The aromatic hydrocarbon dicarboxylic acids of other replacement is as tert-butyl isophthalic acid and M-phthalic acid sulfo group sodium; The cycloalkanes dicarboxylic acids, as 1,4-cyclohexane dicarboxylic acid and isomers thereof and 2,6-decahydronaphthalene dioctyl phthalate and isomers thereof; Two rings and many ring dicarboxylic acids (as norbornane dicarboxylic acids and norbornene dicarboxylic acids, the various isomers of adamantane dicarboxylic acids and bicyclooctane dicarboxylic acids); The condensed ring aromatic hydrocarbon dicarboxylic acids of alkane dicarboxylic acids (as decanedioic acid, adipic acid, malonic acid, butanedioic acid, glutamic acid, azelaic acid and dodecanedicarboxylic acid) and various isomeries (as, indenes, anthracene, benzanthracene (pheneanthrene), benzo naphthalene, fluorenes etc.).Perhaps, can use the Arrcostab (as dimethyl terephthalate (DMT)) of these monomers.

Suitable dihydroxylic alcohols comonomer comprises, but is not limited to, the alkane glycol of straight or branched or glycol (such as, ethylene glycol, propane diols is as 1, ammediol, and butanediol is as 1, the 4-butanediol, pentanediol such as neopentyl glycol, hexylene glycol, 2,2,4-dimethyl-1,3-pentanediol and more senior dihydroxylic alcohols), the ether glycol is (as diethylene glycol (DEG), triethylene glycol and polyethylene glycol), alkanediol such as 3-hydroxyl-2,2-neopentanoic acid 3-hydroxyl-2,2-dimethyl propyl ester, the cycloalkanes glycol is as 1,4-cyclohexanedimethanol and isomers thereof and 1,4-cyclohexanediol and isomers thereof, two rings-or encircle glycol (as the tristane dimethanol of various isomeries more, the norbornane dimethanol, ENB dimethanol and bicyclooctane dimethanol).Aromatic diol is (as 1,4-benzene dimethanol and isomers thereof, 1,4-Benzenediol and isomers thereof, bis-phenol is such as bisphenol-A, 2,2 '-dihydroxy connection and isomers thereof, 4,4 '-dihydroxy methyl biphenyl and isomers thereof and 1,3-two (2-hydroxyl-oxethyl) benzene and isomers thereof) and the lower alkyl ether or the diether of these dihydroxylic alcohols, as the dimethyl ether or the diethyl ether of these dihydroxylic alcohols.

Also can use polyester molecule to have the trifunctional or the multifunctional comonomer of branched structure.They can be the forms of carboxylic acid, ester, hydroxyl or ether.Example includes, but is not limited to, trimellitic acid and ester thereof, trimethylolpropane and pentaerythrite.

The comonomer that is suitable for also has the monomer of mixed functionality, comprises trifunctional or the multi-functional comonomer such as the 5-hydroxyl M-phthalic acid etc. of hydroxycarboxylic acid such as 6-hydroxyl-2-naphthalene-carboxylic acid and isomers and mixed functionality.

PETG (PET) is to have obvious positive stress optical coefficient, can keep birefringence effectively after stretching, and in visibility region seldom or the another kind of material that does not absorb.Therefore, in some purposes of the present invention, can use this material and this material to use the copolymer of high PET content of above-mentioned comonomer as first kind of polymer.

When selecting poly-naphthalene dicarboxylic acids ester (as poly-2,6-(ethylene naphthalate) (PEN) or poly-2,6-naphthalenedicarboxylic acid butanediol ester (PBN)), can there be several method to select second kind of polymer as first kind of polymer.To one of some purposes more excellent method is to select copolymerization naphthalene dicarboxylic acids ester (coPEN), and its preparation makes and seldom forms when stretching or form dielectric grid not.This can be by selecting comonomer and their concentration in copolymer, eliminates or obviously reduce the degree of crystallinity of coPEN and reach.Typical prescription uses the dimethyl terephthalate (DMT) of the naphthalene diformic acid dimethyl ester of about 20-80 mole % and 20-80 mole % or DMIP as dicarboxylic acids or ester component, and makes spent glycol as diol component.Certainly, the dicarboxylic acids of available correspondence replaces this dibasic ester.The number of comonomer that can be used for second kind of polymer formulators of coPEN is unrestricted.The comonomer that is applicable to second kind of polymer of coPEN comprises, but is not limited to, above listed all comonomers that are suitable for the PEN comonomer, comprise the monomer that acid, ester, hydroxyl, ether, trifunctional or multifunctional and mixing official can types.

Isotropic refractive index of second kind of polymer of prediction coPEN usually is useful.The volume averaging value that has found that used refractive index monomer is a proper index.Similar techniques well known in the art can be used for from the vitrification point of second kind of polymer of vitrification point estimation coPEN of the homopolymers of used monomer.

In addition, have vitrification point compatible and refractive index and also can be used as second kind of polymer similar in appearance to the Merlon of the isotropic refractive index of PEN with PEN.

Second kind of polymer also needs not be copolyester or Copolycarbonate.Also can use polyvinyl and the copolymer made by monomer (as vinyl naphthalene, styrene, ethene, maleic anhydride, acrylate, acetic acid esters and methacrylate).Also can use the condensation polymer except that polyester and Merlon.Example comprises: polysulfones, polyamide, polyurethane, polyamic acid and polyimides.Naphthylene group and halogen (as chlorine, bromine and iodine) are suitable for and in advance the refractive index of second kind of polymer are brought up to a desired level of wanting.When needs reduced refractive index, acrylate-based and fluorine was useful especially.

From the front as seen, the purposes of described multi-layer optical film is not only depended in the selection of second kind of polymer, but also depends on that the material for preparing first kind of polymer is selected and used process conditions when stretching.Second kind of suitable polymeric material comprises, but be not limited to, PEN (PEN) or its specific isomers are (as 2,6-, 1,4-, 1,5-, 2,7-, with 2,3-PEN), poly terephthalic acid alkane diol ester is (as PETG, polybutylene terephthalate (PBT) and poly terephthalic acid 1,4-cyclohexane diol ester), other polyester, Merlon, polyacrylate, polyamide is (as nylon 6, nylon 11, nylon 12, nylon 4/6, nylon 6/6, nylon 6/9, nylon 6/10, nylon 6/12 and nylon 6/T), polyimides (comprising TPI and polyacrylamide imines), polyamide-imides, polyether-amide, polyethers-acid imide, polyaryl ether (as polyphenylene oxide and cyclosubstituted polyphenylene oxide), PAEK is (as polyether-ether-ketone (PEEK), aliphatic polyketones (as the copolymer and the trimer of ethene and/or propylene and carbon dioxide), polyphenylene sulfide, polysulfones (comprising polyether sulfone and polyarylsufone), random polystyrene, syndiotactic polytyrene (sPS) and derivative thereof (as the polydichlorstyrene of a rule poly alpha methylstyrene and a rule), the various blends of these polystyrene (to each other or with other polymer, blend as polyphenylene oxide), the various copolymers of these polystyrene are (as SB, SAN and acrylonitrile-butadiene-styrene-terpolymer), polyacrylate is (as PMA, polyethyl acrylate and butyl polyacrylate), polymethacrylates is (as polymethyl methacrylate, polyethyl methacrylate, polypropylmethacryla,es and polyisobutyl methacrylate), cellulose derivative is (as ethyl cellulose, cellulose acetate, cellulose propionate, acetylbutyrylcellulose and celluloid), and polyalkylene polymer (such as polyethylene, polypropylene, polybutene, polyisobutene and poly-(4-methyl) amylene), and fluoropolymer and copolymer (as polytetrafluoroethylene (PTFE), poly-trifluoro-ethylene, polyvinylidene fluoride, polyvinyl fluoride, fluorine-containing ethylene-propylene copolymer, perfluoroalkoxy resin, polytrifluorochloroethylene, polyethylene-copolymerization-trifluoro-ethylene, polyethylene-copolymerization-CTFE), chlorine-containing polymer (as polyvinylidene chloride and polyvinyl chloride), polyacrylonitrile, polyvinyl acetate, polyethers (as polyformaldehyde and PEO), ionomer resin, elastomer is (as polybutadiene, polyisoprene and neoprene), silicone resin, epoxy resin and polyurethane.

Copolymer also is suitable, such as the copolymer of PEN discussed above and other copolyester that does not contain naphthylene group (it can list from above the polyethylene terephthalate copolymer monomer preparation that is used for PEN obtain).In some applications, particularly when PET is used as first kind of polymer, based on copolyester (coPET) particularly suitable of PEN with the comonomer of listing above.In addition, first kind of polymer or second kind of polymer can constitute by miscible or immiscible mixture by two kinds or more kinds of above-mentioned polymer or copolymer (as, the blend of the blend of sPS and random polystyrene or PEN and sPS).Described coPENs and coPETs can directly synthesize, and maybe can be mixed with granulate mixture, wherein have at least a kind of component to be based on the polymer of naphthalene dicarboxylic acids or terephthalic acid (TPA), and other component is Merlon or other polyester, as PET, and PEN, coPET or coPEN.

To purposes, as the preferential material group of second kind of polymer be between rule ethene aromatic polymer, as syndiotactic polytyrene.Be applicable to that syndiotactic vinyl aromatic polymer of the present invention comprises poly-(styrene), poly-(ring-alkylated styrenes), poly-(aryl styrene), poly-(halogenated styrenes), poly-(alkoxystyrene), poly-(vinyl benzoate), poly-(vinyl naphthalene), poly-(vinylstyrene) and poly-(acenaphthalene), and the hydropolymer and mixture or the copolymer that comprise these construction units.The example of poly-(ring-alkylated styrenes) comprises the isomers of following polymers: poly-(methyl styrene), poly-(ethyl styrene), poly-(propylstyrene) and poly-(butylstyrene).The example of poly-(aryl styrene) comprises the isomers of poly-(styryl phenyl).As for poly-(halogenated styrenes), its example comprises the isomers of following polymers: poly-(chlorostyrene), poly-(bromstyrol) and poly-(fluorobenzene ethene).The example of poly-(alkoxystyrene) comprises the isomers of following polymers: poly-(methoxy styrene) and poly-(ethoxybenzene ethene).In these examples, particularly preferred styrene-based polymer is: polystyrene, poly-(p-methylstyrene), poly-(methyl styrene), poly-(to t-butyl styrene), poly-(to chlorostyrene), poly-(m-chlorostyrene), the copolymer of poly-(to fluorobenzene ethene) and styrene and p-methylstyrene.

In addition, available comonomer prepares the syndiotactic vinyl aromatic copolymer.When the definition syndiotactic vinyl aromatic polymer group the described monomer that is used for homopolymers, suitable comonomer comprises that olefinic monomer is (such as ethene, propylene, butylene, amylene, hexene except top.Octene or decene), diene monomers (such as butadiene and isoprene) and polar vinyl monomer (as the cyclic diolefine monomer, methyl methacrylate, maleic anhydride or acrylonitrile).

Syndiotactic vinyl aromatic copolymer of the present invention can be block copolymer, random copolymer or alternate copolymer.

The syndiotacticity of syndiotactic vinyl aromatic polymer of the present invention and copolymer (being surveyed by 13C-NMR) generally is higher than 75%.Syndiotacticity better is higher than 85% divalence racemic modification (racemicdiad), or is higher than 30%, preferably is higher than 50% pentavalent racemic modification.

In addition, though to the not special regulation of the molecular weight of these syndiotactic vinyl aromatic polymers and copolymer, weight average molecular weight is better greater than 10,000 and less than 1,000,000, better greater than 50,000 and less than 800,000.

Syndiotactic vinyl aromatic polymer and EVA also can polymer blend form use, the blend of vinyl aromatic polymers and disordered structure thing for example, the blend of vinyl aromatic polymers and isotactic works, and with any can with the blend of miscible other polymer of vinyl aromatic polymers.For example, polyphenylene oxide and foregoing many vinyl aromatic polymers have good compatibility.

When with mainly being that uniaxial tension technology is when preparing polarizing coating, better combination of polymers as optics comprises PEN/coPEN, PET/coPET, PEN/sPS, PET/sPS, PEN/Eastar and PET/Eastar, wherein coPEN refers to copolymer or the blend based on naphthalenedicarboxylic acid (as mentioned above), and Eastar is a kind of polymer or copolyester (comprising cyclohexanedimethanol unit and terephthalate units), available from EastmanChemicalCo..When preparing polarizing coating with drawing process, the particularly preferred combination of polymers that is used for optics comprises PEN/coPEN, PEN/PET, PEN/PBT, PEN/PETG and PEN/PETcoPBT, wherein " PBT " refers to polybutylene terephthalate (PBT), and " PETG " refers to the copolymer of the PET that uses second kind of dihydroxylic alcohols (normally cyclohexanedimethanol), " PETcoPBT " refers to terephthalic acid (TPA) or its ester and ethylene glycol and 1, the copolyester of 4-mixture of butanediols.

Under the situation of level crossing or Coloured film, the particularly preferred combination of polymers that is used as optics comprises PEN/PMMA, PET/PMMA, PEN/Ecdel, PET/Ecdel, PEN/sPS, PET/sPS, PEN/coPET, PEN/PETG and PEN/THV, wherein PMMA refers to polymethyl methacrylate, and Ecdel is that a kind of thermoplastic polyester or copolyester (comprise the cyclohexanedicarboxyester ester unit, polytetramethylene ether diol unit and cyclohexanedimethanol unit), it can be available from Eaxtman ChemicalCo.." coPET " refers to a kind of copolymer or blend based on terephthalic acid (TPA) (as mentioned above), " PETG " refers to the copolymer of the PET of a kind of second kind of dihydroxylic alcohols of use (normally cyclohexanedimethanol), and THV is a kind of fluorinated copolymer available from Minnesota Mining and Manufacturing Company.

To the level crossing film, in the direction perpendicular to membrane plane, the refractive index of first kind of polymer and second kind of polymer coupling is preferably sometimes, and it provides constant reflection (in other words, not having Brewster angle) with respect to the angle of incident light.For example, in a certain wavelengths, be 1.76 to refractive index in its plane of PEN of biaxial orientation, and the refractive index on vertical film plane can drop to 1.49.When PMMA was used as second kind of polymer in the sandwich construction, on whole three directions, its refractive index can be 1.495 when identical wavelength.Another example is the PET/Ecdel system, can be 1.66 and 1.51 to the similar refractive index of PET in this system.And the isotropic refractive index of Ecdel can be 1.52.Crucial performance is to a kind of material, compares with refractive index in its plane, and its refractive index perpendicular to the plane must more approach refractive index in the plane of another kind of material.

In other example, need deliberately make the refractive index mismatch of vertical plane.Some examples are included in the sample that has three layers or more multi-layered polymer in the optical stack layer, require in this optical stack layer in the intentional mismatch of the refractive index of vertical plane, have opposite symbol with refractive index mismatch on the direction in the plane.Multi-layer optical film of the present invention better is made of multiple different polymer sometimes.The third or various subsequently polymer can be advantageously between first kind of polymer of optical stack layer and second kind of polymer as adhesion-promoting layer; in the heap layer, be used for the optics purpose as extra play; conduct protection border between the optical stack layer; as the top layer, as official's energy coating or as being used for other purpose.At this moment, the third or various subsequently polymer (if any words) composition unrestricted.Several multiple component structures preferably can be referring to the U.S. Patent application 09/006,118 that is entitled as " multicomponent optical bodies ".

E. film designs and structure

E1. coloured speculum

Principle of the present invention can be used for constructing coloured speculum.Generally, these speculums will present the transmission band to two kinds of polarised lights in the visible range, but reflect two kinds of polarised lights at the remainder of visible spectrum.Herein, by this class speculum is called " filter ".In filter of the present invention, the transmission band moves the function of color as incidence angle.

Example E1-1

Following example has illustrated the process of the blue logical filter of production the present invention.

Use coextrusion processes, on a continuous flat film production line, make and contain 209 layers co-extruded films.This multilayer polymeric film is made by PEN (PEN) and polymethyl methacrylate (PMMACP82).Produce about 209 floor with pay-off (such as at United States Patent (USP) the 3rd, 801, No. 429 narrated), these are coextruded on the water-cooled cast wheel, and with conventional order length adjustment instrument (LO) and stenter equipment to its continuous adjusting.With an extruder, speed with 60.5kg/h, intrinsic viscosity (IV) is sent to pay-off for the PEN of 0.56dl/g (dichloro-benzenes of the phenol of PEN:60 percentage by weight/40 percentage by weights), will be with another extruder, with the speed of 63.2kg/h, transmit PMMA.These melt-flows are directed to pay-off, to make the optics of PEN and PMMA.Pay-off produces 209 layers of PEN that replaces and PMMA, makes two layers of PEN of outside play edge protection interlayer (PBL) by pay-off.The smelting process equipment of PMMA is maintained at about 249 ℃, and the smelting process equipment of PEN is maintained at about 290 ℃; And pay-off, top layer module and mould also are maintained at about 290 ℃.

For the pay-off that is used for every kind of material has designed approximately linear gradient about thickness, make the thicklyest to be about 1.72: 1 with ratio.It is too big that this ratio with ground floor thickness and last layer thickness is designed to 1.72: 1 hardware design, so that can not produce the desired bandwidth that reaches of coloured speculum in this example.In addition, the hardware with so design can produce the blue ribbon edge edge of an inclination.In order to correct these problems, once on pay-off, apply a Temperature Distribution.Heat or cool off portion's section of producing these in the pay-off by selected can the passing through that pay-off is produced, they are thickened or attenuate.To produce acceptable precipitous belt edge edge in blueness one side of the zone of reflections, need this technology.Portion's section of making in the pay-off is heated to 304 ℃, is heated to 274 ℃ and will make the thickest portion's section.Intermediate section is heated between these two limiting temperatures.General effect is to produce a very narrow layer thickness distribution, thereby causes a narrower reflectance spectrum.

After pay-off, the 3rd extruder transmits 50/50 mixture that the PEN by 0.56IV and 0.48IV forms with the speed of about 37.3kg/h, as top layer (they are same thickness in the both sides of optical flow).Use this method, the viscosity on top layer is lower than the viscosity of optics, produces that be made up of coextrusion, stable, a fusion laminar flow thus.So material stream passes through the film mould, and flow on the water-cooled cast wheel that uses about 7 ℃ of water inlet water temperatures.With high pressure pinning system the extrudate pinning to casting wheel, the thickness of pinning metal wire is about 0.17mm, and applies the voltage of about 5.5kV.The pinning metal wire is placed on from about 3-5mm of blank and the place that contact with casting wheel, so that the smooth shape of blank acquisition of casting by operating personnel are manual.

Under about 130 ℃, the casting blank is carried out length adjustment with about 3.8: 1 draw ratio.In stenter, before stretching, in about 9 seconds, film is preheating to about 138 ℃, then under 140 ℃, with the speed cross directional stretch of about per second 60% to about 5: 1 draw ratio.The film that obtains at last has the final thickness of about 0.02mm.Its spectrum is shown in Figure 38.

When vertical incidence, for the p-polarised light, the average transmittance in the stopband is 1.23%.Bandwidth during vertical incidence is about 200nm.The slope of red zone edge edge is about every nanometer 5.5% during vertical incidence.In the time of 60 °, the red zone edge edge slope of p-polarised light is about every nanometer 4.2%, and the blue ribbon edge edge slope of p-polarised light is about every nanometer 2.2%, and the spectrum of Figure 38 is to obtain with the light that is parallel to stenter direction (crossing the direction of blank) polarization.Although can not directly measure the refractive index of the PEN of 1/4 wavelength thickness, believe they should with the refractive index approximately equal of PEN surface tunic.In this example, latter's refractive index is to measure with the MetriconPrism coupler that the Metricon company in new Jew state Pennington city makes.To cross blank (by tentering or TD) direction, the direction of following blank (machinery or MD) (also being referred to as length adjustment or LO direction), and thickness or z-direction of principal axis are measured refractive index.The PEN top layer is respectively nx=1.774 and ny=1.720 in the refractive index of TD and MD direction, and the refractive index of z axle is nz=1.492.By regulating the relative draw ratio of this both direction, can between TD and MD direction, obtain phase isoequilibrium preferably.

Example E1-2

The process that following example explanation is produced green logical filter according to the principle of the invention.

By coextrusion processes, on a continuous flat film production line, make one and comprise about 418 layers multilayer film.This multilayer polymeric film is made with PET and ECDEL9967.ECDEL9967 is considered to based on 1, the 4-cyclohexane dicarboxylic acid, and 1, the copolyester of 4-cyclohexanedimethanol and polytetramethylene ether glycol, it is to have bought from the Eastman Chemicals company in New York Rochester city.With (, being narrated in No. 429) pay-off method as United States Patent (USP) the 3rd, 801 by about 209 floor of extrudate production, from being similar to linear bed thickness gradient to having.

Use an extruder,, intrinsic viscosity (IV) for the PET of 0.6dl/g is sent to pay-off, and is transmitted ECDEL with the speed of about 41kg/h with the speed of about 34.5kg/h.After pay-off, same PET extruder be with total flow 6.8kg/h, the both sides that PET is transmitted extrudate as edge protection interlayer (PBL ' s).So material stream has the multiplier design than the asymmetrical two times multiplier (United States Patent (USP) the 5th, 094, No. 778 and the 5th, 094, No. 793) that is 1.40 by one.The ratio of multiplier is defined as, in trunk line, produce average thickness remove the following ducted average thickness.Selecting this multiplier ratio is in order to stay next spectrum gap between two zones of reflections of two groups of 209 layers of generations.Every group 209 layers all have the approximate layer thickness distribution that is produced by pay-off, and overall thickness scale factors is by multiplier and the decision of film extruding rate.The spectrum of vertical incidence (Figure 39) has two delustring frequency bands, and its thickness weighting center is approximately 450 nanometers and 650 nanometers.635 and 450 ratio is 1.41, and this value approaches desirable multiplier design load 1.40.

ECDEL smelting process equipment maintains about 250 ℃, and PET (optics) smelting process equipment maintains 265 ℃, and pay-off, multiplier, top layer melt-flow and mould maintain about 274 ℃.

In this example, the pay-off that is used for making film is designed to, and provides the thickest and ratio and be 1.3: 1 linear layer thickness distribution under isothermy.In order to obtain less ratio in this example, pay-off is applied a heat distribution.The part of making in the pay-off is heated to 285 ℃, is heated to 265 ℃ and will make the thickest part.In the method, thickness is greater than the thickness with isothermal pay-off operation gained, and the thickest thickness is thinner than the thickness that obtains in isothermal operation.Mid portion is arranged to follow at two linear temperatures between extreme distributes.Total effect is to obtain a narrower layer thickness distribution, thereby causes narrower reflectance spectrum.Some thickness errors are introduced by multiplier, and are the reasons of the medium and small difference of spectral characteristic of each zone of reflections.Regulate the speed of casting wheel, so that last film thickness is accurately controlled down to last color.

After multiplier, with the speed (total) of about 28kg/h, add the PBL (top layer) of thickness symmetry, this speed is that the 3rd extruder provides.After this, material flows through a film mould, leads on the water-cooled cast wheel.Inlet water temperature on the casting wheel is about 7 ℃.With a high pressure pinning system the extrudate pinning to casting wheel.The thickness of pinning metal wire is approximately 0.17mm, and applies the voltage of about 5.5kV.The operator manually is placed on the pinning metal wire on the point that leaves blank about 3 to 5mm and contact with casting wheel, makes the casting blank have a smooth shape.Order length adjustment instrument (LO) and tentering equipment with routine are regulated the casting blank continuously.Under about 100 ℃, the length adjustment of blank is about 3.3 to extensibility.In stenter, with about 22 seconds film is preheating to about 100 ℃, and along laterally, with the speed of per second about 20% film is stretched to extensibility and is about 3.5.The final thickness of the film that obtains at last is about 0.05mm.

Figure 39 shows the transmitted spectrum of non-polarized light when 0 ° of incidence angle and 60 °.

Figure 18 and Figure 20 show the have thicker degree p-polarization optical transmission situation of similar film of (slower casting wheel speed y leads).Though can not directly measure the refractive index of the PET of 1/4 wavelength thickness, believe that they should be approximately equal to the refractive index of pet sheet layer.In this example, the refractive index of the pet sheet layer of film is nx=1.678, ny=1.642, nz=1.488.Again, there is more approaching coupling in the same with among the example E1-1 as hope between MD and TD refractive index, can regulate draw ratio so, to obtain the film of balance.The isotropic refractive index of Ecdel is near 1.52.With the process conditions in this example, think and compare that Ecdel keeps isotropism substantially with PET.

In this example, near the stopband the 650nm has the bandwidth of 90nm, and has 5.6% average band internal transmission factor.Slope blue and red zone edge edge is respectively every nanometer 3.0% and 1.9%.At 60 ° of incidence angle places, the bandwidth of same stopband is 86nm, and the average band internal transmission factor is 2.6%.Between 0 ° and 60 ° of incidence angles, the slope of belt edge edge is constant substantially.Near the spectrum during for 60 °, 460nm passband has the bandwidth of about 52nm and 72% maximum transmission rate, and slope blue and that red zone edge edge has every nanometer 2.4% and every nanometer 2.9% respectively.

In order in some preferred embodiment of the present invention, to obtain bright heavy shade, concerning colour filter, importantly in passband, have high transmittance, and in stopband, have lower transmissivity.For the birefringence heap layer that has a given z refractive index matching condition with obtains surprising visual effect, this optical stack layer must provide high reflectivity, makes to have only several percentage points even light still less in the stopband by transmission.More suitable is, under the rated designs angle, the average transmittance of colour shifting film in the zone of reflections be less than about 10%, less than about 5% better, be preferably less than about 2%.For good chromatic rendition, preferably the belt edge edge presents higher slope.More suitable is, slope is at least about every nanometer 1%, better greater than 2% of every nanometer, and more preferably greater than every approximately nanometer 4%.

Except that above situation, for good chromatic rendition, it is about 10% that the average transmittance in the stopband should be less than, and do not have the transmissivity peak value greater than about 20% passband in stopband.Be more preferably, it is about 5% that the average transmittance in the stopband is less than, and the maximum transmission rate of passband peak value is about 10% in the stopband.To the restriction of leaking is important, even when putting on the narrow spectrum leakage that may occur in the stopband.When combining such as some herring bone emission source groups such as low-pressure sodium lamp or some fluorescent lamps, most of energy of light source can leak by transmission by the herring bone in the stopband.

For pure color is provided in reflection, the zone of reflections must be narrow relatively, and the outer reflection of band must be less.Can obtain bandwidth and be about reflected colour 100nm, that can connect, red, green or blue.Can obtain bandwidth is the high pure color of 50nm.The 25nm or the littler zone of reflections can produce the color of extreme high purity, and chromaticity coordinates is positioned at the periphery of the CIE colour space.In order in reflection, to obtain these highly purified colors, must or be immersed in the medium of a refractive index coupling by antireflection coating, suppress band external reflectance from air-polymer interface.

Obtain precipitous belt edge edge, can utilize layer thickness distribution with computer optimization, or in the layer thickness distribution design, use as U.S. Patent application the 09/006th, the precipitous thickness distribution of being narrated for No. 085 of frequency band, wherein the name of patent application is called in " blooming with precipitous belt edge edge ".Similarly, in the preferred embodiment of the colour filter with high colour purity, passband should have precipitous belt edge edge.In this embodiment, the slope of the belt edge edge of passband should be at least about every nanometer 1%, can be better greater than 2% of every nanometer, but more preferably greater than every approximately nanometer 5%.In many application, wish that the transmissivity peak value in the passband approaches the transmissivity of hyaline membrane, be about 90%.For narrower passband,, high like this transmittance values can not be arranged if edge slope is too little.Illustrated as this paper example, the passband with 50%, 70% and 85% transmissivity peak value is possible.Bandwidth is narrow when the 10nm, just might provide 25% transmissivity peak value, even 35%.Bandwidth also is possible greater than any passband of 20nm, uses but desirable width will depend on as expected.

E2. coloured polarizer

Can be with the colour shifting film of production of the present invention in one or several regional polarizer effect of spectrum.For example, such film can play the effect about the broadband reflection device of first polarised light in the visible range, (for example play simultaneously about the effect of the narrow logical filter of color transition of second polarised light, transmission on the narrow bandwidth of second polarised light in the spectrum visual field, and in other local reflection of visual field, and the displacement of transmission band on wavelength is the function of incidence angle).The such film of explanation among example E2-1 and the E2-2.

Example E2-1 to E2-3

Under the temperature of 525  (274 ℃),, PEN sent in 224 layers the pay-off with the speed of 81lb/h (37kg/h).Under the temperature of 540  (282 ℃), speed with 117lb/h (53kg/h), to send in the pay-off with ethylene glycol by the copolyester that 70% naphthalenedicarboxylic acid salt and 30% isophthalate are formed, to make the top layer, and under 525  (274 ℃) temperature, with the speed of 115lb/h (52.3kg/h), make optics.The temperature of pay-off remains on 555  (290 ℃).For example E2-1, E2-2 and E2-3 respectively with 20,25 and 30 meters/minute speed casting blank, and in 154 ℃ stenter stove, were stretched to draw ratio 6: 1 with blank, to produce coloured polarizer.

Film in example E2-1, E2-2 and E2-3 is laminated to after the diffuse background of a white, when observing under the transmission situation, when perhaps observing under reflection case, manifests to naked eyes to yellow to blue and dark red to livid purple, livid purple transparent respectively.When polarizer is observed these samples (at this moment, the axis of homology of second polarizer and the axis of homology of coloured polarizer are at an angle of 90), color is more bright-coloured by second (neutrality).And when neutral polarizer being rotated to the axis of homology that makes it when being parallel to the axis of homology of coloured polarizer, white light is by transmission.Figure 40,41 and 42 shows respectively when the E field of incident light and is parallel to draw direction and is parallel to when becoming the non-stretching direction of 0 ° and 60 ° with these films the transmitted spectrum of film among example E2-1, E2-2 and the E2-3.Notice that to blue polarizer, when incident and E field were parallel to draw direction from 0 ° to 60 °, the zone of reflections moved about 90nm, and when the E field is parallel to non-stretching direction, does not have peak value for livid purple.For dark red polarizer to yellow, when incident and E field were parallel to draw direction from 0 ° to 60 °, its corresponding displacement was 65nm, and when the E field was parallel to non-stretching direction, it did not have peak value yet.The scope of the belt edge edge slope of these polarizers is about every nanometer 3%-4% for blue limit, and red limit then is about every nanometer 1.5%-3%.

The combination of E3. coloured speculum and polarizer

In some embodiments of the invention, colour shifting film is used in combination with polarizer.In a specific preferred embodiment, polarizer is a kind of irreflexive inclined to one side film, such as United States Patent (USP) the 5th, 825, in No. 543 people such as () Ouderkirk narration continuously/more penetrate and play inclined to one side film mutually.In this embodiment, colour shifting film is such one type, and it is from the becoming at the transmission of place, oblique angle (at least for some wavelength) for high reflection at the vertical incidence angle.

In a special structure, colour shifting film is such one type, and it shows to such an extent that resemble a speculum at place, vertical incidence angle, but becomes quite transparent at the place, oblique angle, and presents livid purple look; So in conjunction with U.S. Patent application the 5th, 825, the diffuse reflection of the white of describing in No. 543 people such as () Ouderkirk plays inclined to one side film and uses together with this colour shifting film (CSF).Draw at last be combined in vertical incidence the time play broadband mirrors, but () optical wavelength for example, non-livid purple look is carried out diffuse reflection and is risen partially to great majority when the oblique angle.This film is particularly suitable for as safety diaphragm.In a similar structure, same colour shifting film is used (for example: with the type of dichroic dyestuff making) together in conjunction with an absorptive polarizers.When observing under the transmission situation, this film is black when vertical incidence, and becoming then when the oblique angle is coloured polarizer.The final color that certain this combination is presented in face of the observer depends on a series of factor, type and direction such as light source, the character of colour shifting film (comprise to it be tuned to wavelength), and (if having words) scattering degree of providing by polarizer, and the existence of any material and color.

E4. partial polarization device

Principle of the present invention can be used to produce the colour shifting film that plays the effect of partial polarization device on one or several zone of spectrum.For example, this film can be able to be designed to, be parallel to the light of main and less important tensile axis, and the transmissivity of the polarization that is parallel to certain is higher than the transmissivity of cross-polarization at substantially the same wavelength place transmission-polarizing face.The transmitted spectrum of two kinds of polarizations is all as the function of incidence angle and move.Example E4-1 has illustrated such film.

Example E4-1

On flat film production line, made one by coextrusion processes and comprised about 418 layers multi-thin-layer.This multilayer polymeric film is made by PET and ECDEL9967, and PET is outer or " table " layer herein.Produce about 209 floor with (as United States Patent (USP) the 3rd, 801, No. 429 describe) pay-off method by extrudate, make to having an approximate linear bed thickness gradient.

With the speed of about 34.0kg/h, will have intrinsic viscosity (IV) for the PET of 0.56dl/g is pumped into pay-off, and with the speed pumping ECDEL of about 32.8kg/h.After pay-off,,, PET is sent to the both sides of extrudate as edge protection interlayer (PBL) with the total flow of 8kg/h with same PET extruder.Then, this material stream by asymmetrical a, multiplication than the two times multiplier (United States Patent (USP) the 5th, 094, No. 788 and the 5th, 094, No. 793) that is approximately 1.40.The definition of multiplication ratio is, the average thickness of each of producing in the main pipe removes in the following conduit average thickness of each.Select this multiplication ratio, make and between two zones of reflections, stay next spectrum gap by these two groups of 209 layers of generations.Every group 209 layers all have the approximate layer thickness distribution that is caused by pay-off, and overall thickness scale factors is by multiplier and the decision of film extruding rate.

ECDEL smelting process equipment is maintained at about 250 ℃, and PET (optics) smelting process equipment is maintained at about 265 ℃, and pay-off, multiplier, top layer melt-flow and mould all insulation at about 274 ℃.

In this example, the pay-off that is used to make film is designed to provide the layer thickness distribution of a linearity, under isothermy, the thickest and ratio are 1.3: 1.In order to obtain a less ratio in this example, pay-off has been applied a heat distribution.Be used to make part in the pay-off and be heated to 285 ℃, be used to make the thickest part and then be heated to 268 ℃.In this way, thickness is thicker than the thickness of making of the operation of isothermal pay-off, and the thickest thickness is thinner than the thickness of making under the isothermal operation.Mid portion will be set to follow a linear temperature at these two between extreme and distribute.Total effect is to obtain a narrower layer thickness distribution, thereby obtains a narrower reflectance spectrum.

After multiplier,, add thick and PBL (top layer) symmetry from the 3rd extruder with the speed of about 35kg/hour.Then, material stream passes through the film mould, and is added on the water-cooled cast wheel with 13 meters/minute speed.Inlet water temperature on the casting wheel is approximately 7 ℃.With a high pressure pinning system the extrudate pinning to casting wheel.The thickness of pinning metal wire is approximately 0.17mm, and applies the voltage of about 5.5kV.The operator manually is placed on the pinning metal wire on the point that leaves blank about 3 to 5mm and contact with casting wheel, makes the casting blank have a smooth shape.Order length adjustment instrument (LO) and tentering equipment with routine are regulated the casting blank continuously.Make blank pass length adjuster, but do not stretch.In stenter, with about 22 seconds time, the film preheating is arrived about 100 ℃ approximately, with about per second 20% speed, film cross directional stretch to draw ratio is approximately 5 then.Film was heated for 20 seconds in one 121 ℃ zone.The film that obtains at last has the final thickness that is approximately 0.06mm.

On a Metricon, the pet sheet layer is measured its refractive index at the 633nm place.In this was discussed, the x direction was horizontal (draw direction), and the y direction is operating direction (a non-stretching direction), and the z direction is the thickness direction at film.

Sample	nx	ny	nz
				E4-1	1.660	1.573	1.528

Measure, ECDEL amorphous state copolyester has 1.52 refractive index, and under these stretching conditions, its variation can be greater than 0.01.

When detecting by an unaided eye (two kinds of polarised lights), the viridian color transition the when orange colour when this routine film presents from vertical incidence exceeds 50 ° to the visual angle.When being parallel to draw direction by neutral polarizer observation and use by direction, film shows redness.When to the polarizer orientation, make when being parallel to non-stretching direction by direction, film is yellow.Because still there be the poor of refractive index between PET on the non-stretching direction and the ECDEL, so two tangible reflection peaks are still arranged.The center at each peak is relevant with following equation:

λ/z=t ₁+ t ₂=n ₁d ₁+ n ₂d ₂Equation E4-1

The wavelength of λ=maximum light reflection wherein

t ₁The optical thickness of=the first material

t ₂The optical thickness of=the second material

And

n ₁The refractive index of=the first kind of material

n ₂The refractive index of=the second kind of material

d ₁The actual (real) thickness of=the first kind of material

d ₂The actual (real) thickness of=the second kind of material

For ECDEL (material 2), n ₂And d ₂It all is constant.But work as n _1xTo n _2yDuring the substitution equation, the wavelength of reflection is with polarization shift.For example, be 77nm, λ so if the thickness of ECDEL is the thickness of 82nm and PET _xPromptly be for the polarization that is parallel to draw direction reflects the peak wavelength that obtains, perhaps

λ _x=2 (1.66 (77)+1.52 (82))=505nm equation E4-2

Similarly, λ _yBe for the polarization that is parallel to non-stretching direction reflects the peak wavelength that obtains, perhaps

λ _y=2 (1.57 (77)+1.52 (82))=491nm equation E4-3

Because for the polarised light that is parallel to non-stretching direction, _ΔThe Δ n that is parallel to draw direction is 0.132 pair 0.045, so for the peak of polarization parallel in draw direction, reflection peak is much better than.This can produce the peak of a broad, and it makes about 40nm of effective belt edge edge displacement rather than the 14nm that calculates above.For the light that is parallel to draw direction and non-stretching direction polarization, its transmitted spectrum is included among Figure 43 and Figure 44.

E5. film geometry

Can be divided into two kinds of different types to the colour film geometry.First kind geometry is that film is placed on the polyhedron facet, or is placed on such as on the simple curves such as cylinder or cone.Twist in the method that does not have to stretch or can change its optical property with certain under situation of film, can make any in these forms.If make film have basically color uniformly, so any change in color is that to present to observer's various geometric angles by film caused basically.

The second class geometry is that film has different colors in zones of different when observing under the vertical incidence situation.This variable color can provide in extrusion process; Perhaps by the back extrusion process provide, such as the non-homogeneous stretching in the hot forming process so that the match composite curve; Perhaps provide by pattern-making on the zonule of film.Non-homogeneous stretched film or make film easier attenuation in some zone in pattern-making meeting on the film.When this situation of generation, even do not change viewing angle, the change color from a film part to another part also is tangible.

E6. multiple layer combination

If wish, a slice that can make according to the present invention or more the multi-disc multilayer film use together in conjunction with one continuous phase/decentralized photo film, perhaps as its element.Suitable continuous phase/decentralized photo film comprises the type of those narrations in No. the 08/801st, 329, U.S. Patent application people such as () Allen.In this structure, can be stacked other diaphragm, perhaps diaphragm is bonded together, perhaps diaphragm is separated (for example, make they each other in the transmission of optics rather than contact physically).A kind of product that reflecting optics and polarizer are combined can be used to increase total reflection, still transmitted light is risen partially simultaneously.

Another kind method is, produces single coextrusion sheet, has the film that can select reflectivity properties and polarization properties with formation.For example, can construct a multiple layer combination, wherein some is designed on the required spectrum of a part to be polarization, be speculum (for example, mirror coating have the spectrum that is polarized intentional obstruction leak) and other are designed to peripheral part at required spectrum.So the color of the polarised light of transmission will change with the visual angle.When two identical materials when identical polarization axle is arranged, their performance is similar to other material piece (if reflectivity is very high).If become crossing condition to arrange, they show as the speculum of colourless (silvery) so.Therefore, they provide a kind of method that does not need additional detected equipment and test in Secure Application.

Can so select two groups, make under same process conditions, first group produces speculum, and second group of generation polarizer.For example, speculum can be made by expanded material (wherein at least one is birefringent) (for example, biaxial stretch-formed) on the direction in two planes.Polarizer also can be used two or more stretching step, and the stretching birefringent material is made on the direction in two planes.Be called in name in No. the 09/006th, 455, the U.S. Patent application of " blooming and manufacturing process thereof ", narrated a kind of method of making this form polarizer.Polarizing coating can be a multilayer heap layer, or one deck or more multi-layered continuous phase/decentralized photo film.Therefore, can come, some film is made speculum, and other film is made polarization with the drawing process in two steps.

In general, can be with system in combination narration, that be suitable for making biaxial stretch-formed polarizer in No. the 09/006th, 455, arbitrary system above-mentioned, as to be suitable for making colour shifting film and the U.S. Patent application.Therefore, can make a coextrusion monolithic, it comprises the mirror system and the second polarizer system of first reflection.A kind of useful especially mirror system comprises PEN or contains the copolymer of PEN subunit that as indicated above, conduct has the material of high birefringence after stretching.Again, can be used as second kind of material such as suitable polymers such as copolyester with low-refraction or PMMA.One useful especially polarized systems comprises the multilayer heap layer of a PEN (copolymer that perhaps, mainly comprises the PET subunit).Be that second system makes under the process conditions of a good biaxial stretch-formed polarizer, aforementioned first system will form a good biaxial stretch-formed speculum.In addition, can be on demand, PET is directed to different angles with z-refractive index coupling or mismatch.Under the situation of mismatch, usually imagine PET and have higher value than PEN.

Another kind of useful especially, can be with second system of first system, coupled of using PEN the front narrate continuous/the decentralized photo system (for example, the sufficiently high PEN of molecular weight, or on the contrary to the coPEN of continuous phase, molecular weight is enough low), so handle the synthetic monolithic of forming by these two systems, make the stretching step of winning allow continuous phase/dispersion phase system be in the state of low optical orientation, but regulate first system fully, make to be that second drawing process of two system orienteds can produce first mirror system and second polarized systems now in monolithic.For the ease of coextrusion, second system can be located as surface or nearly skin.Under latter event, outermost layer is the lower PEN of one deck molecular weight, and it is auxiliary and protective layer as coextrusion, in order to avoid cling roller or intermediate plate in drawing process.

In a specific example of present embodiment, optical bodies is made of a multilayer film, and wherein each replaces between PEN and co-PEN.Some PEN comprises the decentralized photo of syndiotactic polytyrene (sPS) in PEN matrix.Because leaking light, the layering of scattering thing or field trash reach balance at last, so it is the control aspect bed thickness is inessential, more tolerant to the variation of film on technological parameter.

Arbitrary material of mentioning in the past all can be used as any of this embodiment, perhaps as continuous phase or decentralized photo in certain certain layer.But special hope can be with PEN and the co-PEN major part as adjacent layer, because the viscosity that these materials can improve layer.

In addition, in layer structure, the variation of many quantity can be arranged.Therefore for example, can follow a repeating sequences making in part or total.Wherein an example is one and has ... ABCB ... the structure of pattern, wherein A, B are different materials with C, or the different compounds of identical or different material, and an one or more decentralized photo and at least one continuous phase of comprising at least among A, B or the C.The material that the top layer is preferably identical or chemically similar.

Isotropism/birefringence membrane stack the layer of combination

Multilayer heap layer of the present invention also can combine with the multilayer heap layer of prior art, to produce some uncommon angular effect.For example, can be with isotropic heap layer to birefringence Coloured film plated film of the present invention, coextrusion or stacked, birefringence Coloured film wherein of the present invention is when vertical incidence, concentrated one or more transmission peaks at given wavelength place, and isotropic heap layer reflects at those given wavelength places when vertical incidence.When all visible wavelengths by this object reflex time that makes up, it is when vertical incidence such as same speculum completely.But at the place, oblique angle, isotropic membrane will leak the p-polarised light, allow to see the transmission peaks of birefringent film.For the isotropism membrane stack layer with Brewster angle, maximum efficiency appears at place, an angle of squint, perhaps near it.

E7. in repetitive, have two-layer incessantly

Though the optical stack layer that is comprised among the many embodiment of the application only have by kind of a different materials (in other words, having an AB cellular construction) form alternately, the present invention also will design the heap layer that uses three kinds or more kinds of materials.Thereby, can produce colour shifting film with ABC or ABCB unit, this film all keeps excitation and colour saturation in all incidence angles, although color is duplicate with the variation of angle and the heap layer of two kinds of material compositions certainly.The material that is used for these structures can come out from different monomer derived, and perhaps the material of two or more can be from identical monomer but derived out with different ratios.Thereby for example A may be PEN, and B may be different other coPEN of level with C, and they differ from one another in the ratio of existing phthalic acid.

The cardinal principle of these structures is similar to the principle of bi-component stack of cells layer: promptly, for the p-polarised light, effective Fresnel reflectance factor of multicomponent unit is not changed with incidence angle.In the system of two kinds of material components, this is to realize by the z refractive index of mating two kinds of material components.When three kinds or more kinds of material are arranged in the unit, the z refractive index that preferably still can mate all material, but not necessarily always possible or feasible.But the z refractive index can be proofreaied and correct (wherein said symbol is that the difference of refractive index is relevant in the face) by the mismatch that has contrary sign at another kind of material interface place in the mismatch at a kind of material interface place.

With the example of ABCB repetitive structure as 1/2 wavelength units, wherein A is the highest material of refractive index in the face, and c is the minimum material of refractive index in the face, if the z refractive index mismatch at A/B interface, so by selecting material C, make the B/C interface have the mismatch of opposite in sign, make the effective Fresnel reflectance factor in unit is not changed with incidence angle basically.The required relative size of relevant two z refractive index mismatches depends on the size of refractive index mismatch in the face.If the equal and opposite in direction of refractive index mismatch in the face of A/B and B/C, the z refractive index mismatch should be equal and opposite in direction and opposite in sign so.In general, when interior face to face difference (A/B and B/C) was unequal, the necessary z refractive index difference of so selecting made in interested angular region or in the angular region of opposite in sign, effectively the difference of interfacial refraction rate is equal approx.Birefringent effective refractive index is derived as in this plane and the algebraic function of z refractive index.

E8. with the diffuse reflection substrate combination

Can colour shifting film of the present invention and various substrate be stacked, bonding or optical coupled, to obtain special optical effect, this especially depends on the color and its optical property (for example, whether it mainly carries out minute surface reflection or diffuse reflection) of substrate.Therefore, for example can be colour shifting film of the present invention gummed, stacked or paste card stock, paper, on the surface of white, perhaps such as on the diffuse reflection surfaces of describing in No. the 08/807th, 930, U.S. Patent application people such as () Allen such as diffuse reflection optics film.Similarly, can use such as various materials such as spray paint, gas deposition metal, metal oxide, metallic salts and apply colour shifting film of the present invention, to obtain various optical effects.The observed optical effect of gained article is especially depended on the light source (for example, surround lighting, polarized light source, ultraviolet source etc.) of these article that are used for throwing light on.

Figure 45-47 shows when colour shifting film of the present invention and various substrate is stacked and viewed optical effect when watching under reflection case.By with colour shifting film of the present invention with such as card stock, white surface or other diffuse reflection surface stacked, can produce the display that color changes as angle function.For example, the described green of example E1-2/dark red colour shifting film and white card material are made the optical bonding of cleaning, and under indoor environment light, watch.When direct viewing, when promptly membrane plane was perpendicular to observer's sight line, normal white card showed emerald green.When card turned over about 60 ° from the upright position, card showed peony.

The benefit of diffuse reflection substrate is that the color that this substrate appears film scatters the plane of incidence that coloured light is arranged (perhaps reflecting away with different angles of reflection) that is reflected by film mirror in the plane of incidence.Thereby, can allow the beholder distinguish by transmission and color that be reflected.Can only see the specular light line in a direction.But, can the either party's parallactic angle around the diffuse reflection cone see diffuse light, wherein the half-angle of cone equals incidence angle θ.At other incidence angle and angle of reflection place, can see other color.

Figure 46 shows the optics behavior of watching when stacked when colour shifting film of the present invention and a black surface in reflection.Figure 45 is pointed as reference, is difficult to reflective is observed the reflection colour of film, because eyes must be placed on the position of specular reflectance beam, any light that it can be transmitted by film is simultaneously cheated.If, can only see its reflection colour so coloured being laminated on the black surface of reflection.Therefore, (for example, black the benefit of) substrate is, is mainly determined by the electromagnetic radiation wavelength that film optical stack layer is reflected from the observed color of this object in high absorption.

Figure 47 shows the optics behavior of watching when stacked when colour shifting film of the present invention and mirror surface in reflection.Here, from the film mirror beam reflected will with combine from mirror surface minute surface beam reflected, to provide the color same with incident beam.The Coloured film that is laminated to high reflection surface, broadband will be with color, because the beholder can see the color that all are reflected.In the present embodiment, can from reflected by objects spectrum, remove in the electromagnetic radiation at first by some wavelength of colour shifting film transmission with coloured speculum or colour filter.

In addition, the diffuse reflection medium can be a kind of irreflexive polarizer, and it comprises having continuous phase and decentralized photo simultaneously, and with the color transition multi-layer optical film pairing of minute surface reflection, and the latter can be or be not polarizer.Under the situation of using layering polarizer and diffusion polarizer, in some applications, preferably make each polarization by reflection axle quadrature.As shown in figure 48, layered membrane reflects a polarization with minute surface, and a kind of color relevant with angle is provided, and diffuser will reflect the polarization of quadrature.A kind of pigment can be infiltrated in the diffuser, make that when the color characteristics of mirror film changed, the color of diffusion part remained unchanged, thereby a very unique colour shifting film is provided.In certain embodiments, in the side of diffusion polarizer, absorb any transmitted light with a black back to layered membrane.

By a scattering medium being placed on a side of colour shifting film, and from opposite side with diffused light source this film that throws light on, the optical effect that can obtain adding.In general, scattering medium only need carry out optical communication with film, and leans on enough closely with film, makes light after passing through film, with sufficient angular region directive scattering medium.But, if desired, can be by the suitable bonding air interface of eliminating between film and the scattering medium.By suitable selective scattering medium, when watching in transmission, treated and untreated zone will show as different colors in the film.

For example, if in vertical incidence (0 °) when locating to measure colour shifting film, this film has a narrow transmission band in the red color area of spectrum, if and shine this exposed film with diffused light source, then when it shows redness when an angle is watched, and that described angle position is a straight line from beholder to the film is vertical with the plane of film.When the visual angle changes over the more approaching plane that is parallel to bare membrane of straight line from beholder to the bare membrane, observing color will change green into from redness.But if a blank sheet of paper is put into film away from light source one side, when watching in transmission, the part that is covered by paper in the film all manifests yellow green in any angle so.If a brightness enhancement film is placed on the side that film deviates from light source, in transmission with certain angle (straight line from the beholder to the BEF/ film composition is perpendicular to membrane plane) when watching, it is green that the part that is covered by BEF in the film is, and when visual angle change made from the observer to the straight line of BEF/ film composition the more approaching plane that is parallel to the BEF/ film composition, color transition became orange colour/redness.Described brightness enhancement film can be bought to the 3M company in Minnesota State Paul city, and production code member is BEF.

Example E8-1 is to E8-6

Below some examples illustrated when colour shifting film of the present invention combines with various scattering mediums, and under the transmission situation observed optical effect.

In example E8-1, adopted the sample of a colour shifting film, it has by replacing that PEN and PMMA form.Film among its preparation method and the example E1-1 is roughly the same.The difference of the film of example E8-3 and the film of routine E8-1 only is, be that it is that edge (opposite at the center) from blank scales off, compare film transmission value under the vertical incidence situation when the blank center scales off, the fine difference of its directed number of degrees and/or layer thickness distribution have caused moving of its transmission peaks width when vertical incidence.Film among the example E8-5 be use with example E8-1 in the same quadrat method of film make, but the speed of casting wheel is fast slightly.

Every sample is placed on the diffuse background light of Graphiclite D5000 Standard Viewer, and with a transmission of using the spectrophotometer measurement sample of fiber optic collector, wherein the numerical aperture of fiber optic collector is 0.22.Directly optical fiber is placed on the film perpendicular to the plane of membrane sample, thus allow light from light source by exposed film, the angle that is no more than 25 ° with relative normal direction enters optical fiber.If independent measurement is backlight, the baseline that is used in all wavelengths so and all is-100% transmission is measured the bare membrane sample.If, also can in the colour space of L*, a*, b*, calculate color value to sample with a small-sized fluorescent lamp bulb illumination.When vertical incidence, example E8-1, the film of E8-3 and E8-5 presents blueness respectively, and is dark red and yellow.

In example E8-2, E8-4 and E8-6, the standard blank sheet of paper of one 8.5 * 11 size (can be bought to BoiseCascade company, production code member is X-9000) be placed on respectively on the film of example E8-1, E8-3 and E8-5, the transmissivity of measuring vertical angle, and calculate color value once more.Example E8-1 lists among the table E8-1 to the color value of E8-6.The transmission value of sample E8-1 and E8-2 is shown among Figure 49, and the transmission value of sample E8-3 and E8-4 is shown among Figure 50, and the transmission value of sample E8-5 and E8-6 is shown among Figure 51.

Table E8-1

Sample	Film color during vertical incidence	With paper?	C* ?	A* ?	B* ?	Subjective colo(u)r
							E8-1	Blue	Do not have	32.4	0.1	-126.3	Blue
E8-2	Blue	Have	48.8	23.8	-23.4	Pink/dark red
							E8-3	Dark red	Do not have	59.5	66.7	-55.6	Dark red
E8-4	Dark red	Have	60.5	6.3	27	Yellow/orange colour
							E8-5	Yellow	Do not have	91.3	3.5	130.3	Yellow
E8-6	Yellow	Have	66.8	-1.9	26.8	Yellow

As show shown in the result among the E8-1, and in the spectrum shown in Figure 49,50 and 51, when a blank sheet of paper was placed between film and the detector, blue, dark red and yellow film can change color.As shown in top several examples, when watching blank sheet of paper/film combination, the amount of change color especially depends on the bandwidth of colour film and the position at its place in spectrum.When watching in paper/film combination, peony and blue film present obvious color and change, and yellow film is not.The composite type of paper/film is useful in such as application such as commercial picture (back lighting), security applications and decorative lighting application.

When film of the present invention and light source optical coupled, and when between film and light source, putting into the scattering media, can obtain other optical effect.Although these embodiment generally require needn't require film to contact with diffusion medium physics in all embodiments scattering medium and film optical coupled.In these embodiments, when the oblique angle is watched, in the film with the zone of scattering medium optical coupled than not having the zone of optical communication brighter with scattering medium in the film, and color is slightly different.

Example E8-7 is to E8-12

Following Example illustrated when putting into scattering medium between light source and the colour shifting film of the present invention, and viewed effect when watching film in transmission.

In example E8-7, E8-9 and E8-11, it is on 2100 the 3M2150 overhead projector light source that the sample that is made of PEN/PMMA multilayered color-forming shifting film is placed on a model, and watches sample in transmission, directly watches the objective table of overhead projector.The film of example E8-7 and E8-9 is identical with example E8-3 and E8-5's.Film among the example E8-11 is used with routine E8-1 similar methods and is made, but the speed of casting wheel is slower.When watching in transmission under the situation in vertical incidence, that the film of example E8-7, E8-9 and E8-11 presents respectively is dark red, yellow and livid purple look, and when when watching in transmission under the oblique angle situation, presents yellow, transparent and navy blue respectively.

In example E8-8, E8-10 and E8-12, repeat the process of example E8-7, E8-9 and E8-11 respectively, specifically the standard blank sheet of paper of one 8.5 * 11 size (can buy to BoiseCascade company, production code member is X-9000) be placed on each membrane sample below.Cut out paper smallerly than sample, the profile that makes every kind of paper/film be combined in the transmission can be compared with the profile of film itself.When watching with side by side paper of bare membrane/film combination, the color of paper/film combination seems different with bare membrane.Give one example, the brightness of paper/film combination is different with bare membrane.Its result summarizes in table E8-2.

When sample E8-8 and E8-10 are watched in the oblique angle, between film and light source, there is the part of paper to have different colors in the sample than the part of no paper between film and light source.Under the situation at oblique angle, sample E8-8 shows green-yellow when paper is arranged, and when not having paper for yellow.Example E8-10 shows purple-white when paper is arranged, and is transparent when not having paper.When sample E8-12 is watched at the oblique angle, partly to compare with no paper, it is different with brightness that the color of paper part is arranged.For the part that paper is arranged between film and light source, it is bright dark red that color is, and the part of not having paper is navy blue.

Table E8-2

Sample	Is there there paper?	Color during vertical incidence	Color when the oblique angle
				E8-7	Do not have	Dark red	Yellow
E8-8	Have	Dark red	With green yellow
				E8-9	Do not have	Yellow	Transparent
E8-10	Have	Yellow	Purple white
				E8-11	Do not have	Livid purple	Navy blue
E8-12	Have	Be with the livid purple of Huang	Bright dark red

On the substrate that colour shifting film is placed on black or white, or with the adhesive of filling black or Chinese white, can also be with colour shifting film with coloured substrate or have that the substrate of its gray scale combines between the black and white.This coloured substrate can be opaque (basically not transmitted light), translucent (diffuse transmission, the optical hazes of the different amounts of band), or transparent (transparent to some color, as promptly not have the transparent of diffuser, but color is arranged).

Green logical filter among the example E1-2 is combined with transparent coloured substrate, obtain three examples.When vertical incidence, green logical filter transmit green, and reflection peony (blueness and red wavelength).When wide-angle incident, the color quilt conversely.Green logical filter applications redly, on the plastic foil of yellow and blueness in transparent (non-diffusion).Film/coloured substrate combination is placed on a blank sheet of paper, (sticking one side of film with clear binder) watches on one side from the front, every kind of film presents a kind of in two kinds of colors near vertical incidence the time, it depends on specular light line or the transmitted lights whether eyes have seen that great majority are scattered out by paper:

Red substrate: dark red or dim metallike look

Yellow substrate: coppery or green

Blue substrate: dark red or blackish green

When film was used in combination with coloured substrate or grey substrate, observed effect was between white and black substrate, and it has the eyes of obscuring the beholder is the tendency of " really " color about for what.These class article have its use in the display of guiding notice.

When (by coloured substrate) when watching from behind, top sample has following phenomenon:

Red substrate: redness, on arbitrary background or substrate

Yellow substrate: being coppery when on dark substrate, is peony in the time of on white background

Blue substrate: being purple when on dark-background, be green in the time of on white background.

E9. with the combination of minute surface reflective

As previously mentioned, film of the present invention can make up with speculum (the particularly speculum in broadband) and other reflective, to obtain an object that can show the 3 dimension degree of depth.Film and speculum are arranged to approximate parallel but separate a bit of distance, can obtain this combination easily like this.Although all can be observed this effect with any mirror substrate, but preferably use mirror coating pliable and tough, polymer, because this class mirror coating is pliable and tough as to be enough to folding, waviness, or the formation pattern, make the object that obtains at last present the wave effect of reinforcement 3 dimension effects.In an example, with CSF of the present invention be tuned to blue spectral region, this colour shifting film is pasted on pliable and tough, the broadband mirrors film.The size of this broadband mirrors film is more bigger than CSF's.So film is pasted, makes its both sides alignment, thereby the space is introduced in the broadband mirrors film.Because mirror substrate provides different incident angles, so the film that obtains at last reflects various bluenesss, and presents corrugated profile, have a few the surface of picture storage cistern.For example this class film can be as decorating backing in the aquarium.

Can in all sorts of ways provides the space between CSF and mirror substrate.Therefore, for example can be placed on the transparent net of a part between CSF and the mirror substrate.Another kind method is, as United States Patent (USP) the 5th, 783, No. 283 (people such as Klein) is described, and the degree of crystallinity of colour shifting film and/or mirror substrate is controlled, and makes one or two polylith shape in these surfaces.

E10. non-film optical bodies

Although described the present invention repeatedly with regard to blooming here, Xu Shu principle and consideration here also can be used for making a variety of other optics that are not considered film.For example, can use principle described herein, from multi-layer resinous stream, produce the hot forming or the molded article of many kinds of color transitions.Can be split into little shiner to film of the present invention, it can be used as free-pouring composition, perhaps by disperseing in solid (for example, solidified plastic resin) or liquid (for example, the coating composition) matrix.Also film can be cut into the bar of virtually any size, at one end knotting (as in pom-pom pom-pom) or interweave.

E11. number

Film of the present invention generally comprises 10 to 1000 layers.For the reflector of single herring bone, its scope should be preferably between 20 and 100 layers between 10 and 200 layers.High/low refractive index is that 50 layers of heap layer of 1.75/1.50 will produce a high reflectance zone (99% reflection peak), has about 10% fractional bandwidth FWHM (overall with at half maximum place).If the difference of refractive index has reduced decimal x, then quantity must increase 1/x, to keep identical reflectivity.Bandwidth is also narrow decimal x, and in order to keep identical bandwidth, number must increase about 1/x again.

One cold reflector generally has between 100 and 1000 layers according to using.To the application on the gardening, for example 90% reflectivity is acceptable, and can even may preferentially select for use for the price reason, just can realize because it only needs about 200 layers.Reflectivity is reached 99%, and general at least 500 layers are only desirablely, although this number can rely on the selection of material theatrical change are arranged.If for example this application is that the tendency of PEN experiences the ultraviolet yellowing and will become problematic (and if this use use of getting rid of ultraviolet absorption device or disabler), so available PET/coPET replaces, but for similar reflectivity will be at least about 1000 layers.

To a herring bone visible light transmission filter, its desirable scope is between 100 and 1,000, the most preferably between 200 and 500.To having the gardening film of green reflector heap layer and infrared reflective device heap layer.Its desirable scope is between 200 and 1000 and the most preferably between 400 and 800.Be transferred to the ir reflector film of wavelength beyond 1100nm and surpass 1000 layers possibly, if particularly the design of their heap layer comprises in optical repeat unit more than 2 layers in order to suppress the more senior zone of reflections.

F. special

F1. top layer

The non-optical of a kind of material may be configured on one or two main film surface with being coextended, in other words Ji Ya optical stack layer.Composition be also referred to as the top layer can selected conduct, for example protect the complete of optics, add character machinery or physics for the film that obtains at last or add function for the BM that obtains at last.Suitable material in the selection may comprise one or more kind materials of optics.Having to by the optics that overstocks other material of similar melting viscosity being arranged may also be useful.

The broad scope of the shear strength that the multilayer heap layer that top layer or multilayer may reduce to be extruded may particularly be exposed in mould in extrusion process.High shear environment may cause undesirable distortion in optics.In other words, if the localized variation of color is a desirable effect, the distortion that can do to decorate can be by the viscosity of the mismatch of optics and/or top layer, or almost there is not or do not have the technology on top layer to produce, so that some bears local thickness's distortion at least, cause the effect of doing to decorate that scenery is arranged.One deck top layer or multilayer add physical strength or minimizing problem in technology also may for the synthetic that obtains at last.Such as, in orientation process, reduce the tendency that film ftractures for instance.Keep unformed skin-material to have helping make to have more tough and tensile film.But hemicrystalline top layer has and helps make the film with high tensions modulus.Can be other function ingredients such as anlistatig additive, the UV absorption device, dyestuff, antioxidant and pigment are added to the top layer, do not prick the optical property of wishing in the product that obtains at last as long as they do not disturb basically.

Also can add film or device that top layer or plated film obtain to the end, to give the desired barrier properties of wanting.Therefore, for example can barrier film or plated film, as a constituent element in top layer person or the top layer, so as with the transmission property of film or device to changing such as liquid such as water or organic reagent or such as the direction of gases such as oxygen or carbon dioxide.

Adding top layer or plated film also can give or improve anti-punctural and/or anti-tearing property in the object that in the end obtains.Therefore, for example the skin at blooming comprises among the embodiment of coPEN, the coPEN of one deck integral body can with optics coextrusion good tear resistance of film to give to obtain at last.The factor of being considered when the material that has resistance to tearing for selection comprises: elongate fracturing percentage, Young's modulus, tear resistance, bonding with internal layer, transmissivity and absorptivity in interested electromagnetic wave bandwidth, optical clarity or photographic fog, refractive index as frequency function, texture and uneven, melting heat is stable, molecular weight distribution, melt rheology and two extrudability, the speed of the mutual diffusion of miscibility between surfacing and the optical material, viscoelastic response, relaxation under the stretching condition and crystallizing power, heat endurance under serviceability temperature, against weather, adhere to the ability of plated film, and to permeability of all gases and solvent etc.The top layer of anti-punctural and tear resistance can be during process for making or plated film or apply when being laminated to blooming afterwards.Such as with two extrusion processes, during manufacture, these are adhered on the blooming, the benefit of doing like this is to protect blooming during manufacture.In certain embodiments, can provide one or more layers anti-acupuncture or anti-tearing in blooming, wherein blooming can be independent, also can combine with anti-acupuncture or anti-top layer of tearing.

Can be when the extrusion process process, the top layer is applied on several points on the one side of the optical stack layer that pushed or two limits, in other words be extruded withdraw from the extruding mould with the top layer before.The multilayer film that forms before the lamination layer structure on top layer also is possible.The optical thickness on top layer can be distributed in optical stack layer/top layer gross thickness about 2% in about 50% scope.

In some applications, additional can getting on by coextrusion or by adhesion when making blooming in the outside of top layer film.This additional also can in independent coating operation, be extruded or plated film goes to blooming, or as independent film, thin slice, perhaps such as polymer (PET), acrylic acid (PMMA), Merlon, substrates hard or semihard such as metal or glass are laminated to blooming and get on.

The polymer of one very big series is suitable for doing the top layer.Wherein main amorphous polymer, suitable example comprise based on one or more terephthalic acid (TPA), 2,6 naphthalenedicarboxylic acids, and isophthalic acid, the homologue of phthalic acid or their alkyl ether, and such as the copolyester of the alkane glycols of ethylene glycol.It is poly-2 that the semi-crystalline polymer that is applicable to the top layer comprises, 6-(ethylene naphthalate), polyethylene terephthalic acid (TPA) and nylon material.The top layer that may be used to increase the toughness of blooming comprises the polymer such as the high elongation of ECDEL and PCTG5445 (from Yi Siman chemical company, Rochester N.Y. can buy on market) and Merlon.Also can be used for this purpose such as polyolefin such as polypropylene and polyethylene, if particularly they are made and adhere to blooming with phase container.

F2. function

Can add various functions or plated film and change or improve their physics or chemical property, special surface along film or device to blooming of the present invention and device.This or plating can comprise, for example antiseize paste, low viscosity rear-back materials, conduction, antistatic plating or film, stop, flame inhibitor, UV stable device, wear-resisting material, optics plating or for improving the mechanical integrity of film or device or the substrate of intensity.

Handle film of the present invention and optics with low friction plating or slipping agent,, give their good sliding properties such as polymer beads is coated on the surface.Another kind method is to revise the form of these material surfaces by controlling extruding condition, for film provides a smooth surface; United States Patent (USP) the 5th, 753, No. 467 narrations are used for revising the method for configuration of surface.

In some applications, as the place of film of the present invention as an element in the adhesive tape, available low adhesion back sizing material (LAO) plating or to handle film such as those films based on urethanes, silicone or fluorine compounds chemistry may be desirable.So the film of handling presents the proper releasing properties about pressure sensitive adherent phenomenon (PSAs), thereby make might be to them with the adhesive place and in going into tube.Purpose that the adhesive tape of handling like this can be used for decorating or hope will have arbitrary application of diffuse reflection or transmission on the surface of band.

Also can provide one deck or more conductive layer to film of the present invention and optics.This conductive layer can be by such as silver, gold, copper, lead, chromium, lithium.The metal of tin and titanium, such as silver alloy, the metal alloy of stainless steel and chromium lithium ferroalloy or doping or unadulterated tin-oxide, zinc oxide is formed with the metal oxide semiconductor of pluging with molten metal tin-oxide (ITO).

Also can provide antistatic plating or film to film of the present invention and optics.This plating or film comprise, for example V ₂O ₅And sulfonic acid polymer, carbon or other conducting metal.

Also can provide one deck or than multilayer about the barrier layer of the transmission property of some liquid or gas and changing blooming or plating to blooming of the present invention and device.Therefore, for example can be restraining steam, organic reagent, O ₂Or CO ₂Film or the plating of transmission by film offer device of the present invention and film.In infiltration through moisture, the environment of the height humidity that the group light of film or device will be distorted is special down wishes have the barrier layer to plate.

Also available fire inhibitor is handled blooming of the present invention and device, particularly ought be used under the airport environment such as strict fire statute.Suitable fire inhibitor comprises trihydrate, the antimony trioxide of aluminium, the organic phosphorus compound of antimony pentaoxide and delay flame.

Also can provide often the wearability used as the top layer or rigid plating to blooming of the present invention and device.These comprise can be from Rohm8Haas such as polyacrylic hard plating, Philadelphia, acryloid A-11 that PA obtains and Paraloid K-120N such as those at United States Patent (USP) the 4th, 249, narration also can be from Sartomer Corp in 011, the urethanes acrylates that Westchester, PA obtain and from acyclic PIC (for example, Desmodar N-3300, can be from Miles, Iac, Pi Hsbargh, PA obtains) and polyester is (for example, Tone Polyol0305, can be from Union Carbide, Honston, TX obtains) reaction in the urethanes that obtains plate firmly.

Can also further take blooming of the present invention and device layer by force to hard semi-stiff substrate, make them can drawing or opposite such as glass for example, metal, polyacrylic, polyester and other polymer support, form and remain on the shape that a hope is wanted.To some when being used on other frangible support when blooming, then available by PET film or the tear-resistant film of anti-thorn form additional.

Also can provide shatter-proof film or plating to blooming of the present invention and device.Be suitable for the film and the plating of this purpose, for example in patent gazette EP592284 and EP591055, narrate, and can be from 3M company, St.Paul, MN can buy on market.

For the various optics of special application, material and device also may be used on or connect together using the film and the device of invention.These include, but are not limited to light plating commonplace or commonplace; Panel shows and the liquid crystal panel of secret chamber window such as being used for; Photographic emulsion, fiber; Dazzling film such as linear Fei Nieer camera lens; Brightness enhanced film; Holographic film or imaging; But the film of embossing; Resist and smash film or plating to pieces; Infrared transparent film for the low-E application; Release film or release plated film paper and polarizer or speculum.

Attempt the one side of the first type surface of blooming or two-sided on repeatedly additional, and these can be arbitrary combinations of above-mentioned plating or film.For example, when an adhesive is used on the blooming, adhesive 3 can comprise such as the pigment of titanium dioxide increasing whole reflectivity, or it may be optically transparently to get on the reflectivity that allows the reflectivity of substrate be added to blooming.

In order to improve the invertibity of roll shaping and film, film of the present invention also can comprise one and be attached to antiseize paste film or be added to film as an independent plated film.In mostly using, antiseize paste only is added to one side of film, be to be desirable for photographic fog being reduced to minimum this face towards firm substrate.

F3. antireflection

Film and other optics of making according to the present invention also can comprise one deck or more antireflection or plating, dielectric metal oxide or metal/metal oxide blooming such as for example vacuum coating of common usefulness, the solvable silica gel of silica plating and such as those antireflections plated film or extruding that derives from the fluorine-containing polymer compound of low-refraction as THV, can be from 3M company (St.Paul, the squeezable fluoropolymer of MN) having bought.This may be or may not be polarization sensitive or plating as increasing transmission and reducing the reflection high light and can put on film and optics by suitable surface treatment such as plated film or sputtering etching.

In certain embodiments of the present invention, certain polarised light is made to be transmitted as greatly and/or to make minute surface be reflected into minimum be desirable.In these embodiments, optical bodies can be by two layers or form more.Only rare in these one deck is formed with antireflection system that the top layer closely contacts by one.Such antireflection system plays the minute surface reflection that reduces incident light and increases the effect that enters the incident light number of part in the body of forming the optical stack layer.Such function can be finished by a series of methods of knowing in technology.Example is 1/4 antireflection film, two layers or more antireflections heap layer, the refractive index of classification and the opacity of classification.Increase transmitted light if want this anti-reflection function also can be used for the other transmitted light of body.

F4. anti-photographic fog

Can provide the film that can provide resistance to fogging matter or plating to the film of making according to the present invention and other optics.In some example, foregoing antireflection is used as antireflection and the anti-photographic fog character that can give with film or device.The various anti-photographic fog agent of knowing in technology is applicable to the present invention.But in general, these materials are such as substrates such as fatty acid esters, and they give the film surface hydrophobic property, and impel a kind of continuous, transparent quite a lot of moisture film of formation.

Several inventors have reported the plating that can reduce surperficial mist formation tendency.For example, it is mixed to produce the product of an anti-photographic fog that United States Patent (USP) the 3rd, 212, No. 909 (Leigh) have disclosed the amino and a surfactant usefulness sulfuric acid treatment or sulfonic acid processing fat material that use such as the alkyl amino carbonyl acid ester.United States Patent (USP) the 3rd, 075, No. 228 (Elias) disclose the poly-alkoxyethanol of the alkyl-aryloxy that uses sulfuric acid treatment to cross, and have alkyl benzene sulfonate and are used for washing and give kinds of surface with anti-photographic fog character with generation.United States Patent (USP) the 3rd, 819,522 (Zmoda) have disclosed in anti-photographic fog window cleaning agent surface active agent composition, use the surfactant composition of being made up of the derivative of decynediol, and the surface active agent composition that comprises carbonyl ethyl alkylsurfuric acid salt.The special fair 6[1994 of Japan] 41,335 disclosed anti-cloud and mist and water clock constituent that colloid silicon dichloride and a kind of cation A urfactant form by colloidal alumina.United States Patent (USP) the 4th, 478, No. 909 (people such as Taniguchi) disclosed the anti-photographic fog plated film of the sulfuration of extremely target-seeking anti-photographic fog character being made up of the ethanol of tangible importance the weight ratio of a kind of silica of meticulous division and its carbon/silicon of organo-silicon compound.Can be with comprising that the various surfactants of fluorine-containing surfactant improve the surface flatness of plating.In United States Patent (USP) the 2nd, 803,522; 3,022,178 and 3,897, narrated other anti-photographic fog plating for No. 356 in conjunction with Aurfactants.World patent PCT96/18,691 (people such as Schoetg) have disclosed certain methods, use these methods, and plating can provide the character of anti-photographic fog and this two aspect of antireflection.

F5. ultraviolet protection

Ultraviolet film or plating that film of the present invention and optics are crossed by stabilization processes can prevent ultra-violet radiation.The plating of suitable stabilisation ultraviolet film comprises that those contain BTA or hindered amine light stabilizer (HALS) such as Tinuuin292, and the two all can be from CibaGeigy company, Parsippany, and NJ. has bought on market.Suitable in addition stabilisation ultraviolet film and plating comprise that those can be from BASF AG, Parsippany, NJ bought on the market comprise benzophenone or this film of Diphenylacrylate class or plating when lighting apparatus that blooming of the present invention and device are used for outdoor application or go out that remarkable number is in light emitted at the light of spectrum ultra-violet (UV) band the time be particular importance.

G. additive

G1. lubricant

In film process of the present invention (for example, extruding), available various lubricants.Be used for suitable lubricant of the present invention and comprise calcium stearate, the ester acid zinc of waking up, hard ester acid copper, cobaltous octadecanate, neodecanoic acid molybdenum and acetylacetonate ruthenium (III).

G2. antioxidant

Be applicable to that antioxidant of the present invention comprises 4,4 '-sulphur two-(the 6-tert-butyl group-metacresol), 2,2 '-methylene two-(4-methyl-6-tert butyl-butylphenol), 3,5-di-t-butyl-4-hydroxyl hydrocinnamic acid octadecane ester, two-(2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, Irganox 1093 (1979) (phosphoric acid ((3,5-two (1, the 1-3,5-dimethylphenyl)-and the 4-hydroxy phenyl) methyl)-two (octadecane esters)), Irganox1098 (N, N '-1,6-dihexyl two (3,5-two (1, the 1-dimethyl)-4-hydroxy benzenes propionamide), Naugaard445 (arylamine), Irganox L57 (alkylating diphenylamine), Irganox L115 (bis-phenol of sulfur-bearing), Irganox L06 (alkylating phenyl-α-An Jinai), Ethanox 398 (fluorine phosphinate) and 2,2 '-partially ethylene (4, the 6-di-tert-butyl-phenyl) fluorine phosphinate (phosnite).

Antioxidant has sterically hindered phenol preferably, comprise butylated hydroxy-methylbenzene (BHT), vitamin E (two-α-vitamin), Irganox 1425WL (two (adjacent ethyls (3, the 5-di-tert-butyl-4-hydroxyl benzyl) Irganox 1010 (four (methylene (3 phosphonic acids calcium),, 5-di-t-butyl-4-hydroxyl hydrogenated cinnamate)) methane), Irganox 1076 (3,5-di-t-butyl-4-hydroxyl hydrocinnamic acid octadecane ester), Ethanox 702 (bis-phenol of steric hindrance), Etanox 330 (bis-phenol of HMW steric hindrance) and Ethanox 703 (the phenol amine of steric hindrance).

G3. dyestuff, pigment, printing ink

Film of the present invention handled by available printing ink, dyestuff or pigment and optics changes their appearance or changes a social system them by the specification of special applications.Therefore, for example film can with printing ink or its such as be used for showing that product proves, the typographic(al) mark of advertisement, warning, decoration or out of Memory handles.Various technology can be used to print on film, such as screen printing, typographic printing, hectograph, flexographic printing, some mint-mark brush, laser printing or the like, and can comprise a kind of or two kinds of synthetic printing ink with various types of printing ink, the dry printing ink of oxidation drying and ultraviolet, dissolving printing ink, colloidal state printing ink and 100% ink set.

Also can be used on the painted appearance that changes blooming on the film, to blooming, impose a plating of finishing pigment on the surface of blooming, contain a kind of pigment at one or more materials that are used to make blooming such as the film of a stacked dyeing.

Imagined visible in the present invention and far infrared dyestuff and pigment, and comprised, for example such as the Optical Bleaching Agent that in color spectrum, absorbs the dyestuff of ultraviolet and fluorescence.Can add the appearance that other adding change blooming and comprise, for example opaque (black), diffusion, holographic picture or holographic diffuser and metal.Wherein each all can be applied directly to one or two surface of blooming or be laminated to second tunic of blooming or a part of foil construction.In other words, can be included in one deck such as few component parts opaque or diffusion agent or the colorful one pigment and be used for laminated optical film in the adhesive layer on another one surface.

Also can offer film of the present invention and device with metal-plated.Therefore, for example available pyrolysis, powder coating, vapour deposition, cathodic sputtering, the ion implantation method identical with other directly are applied to blooming to a metal.Metal forming or hard metallic plate also can be laminated to blooming and go maybe can utilize technology above-mentioned earlier independent polymer film or glass or plastic sheet to be metallized, and then are laminated to blooming of the present invention and device gets on.

Dichromatic dyestuff is useful especially additive in many application.Since when they by molecule when being arranged in the material, they absorb the ability of a particular polarization light.They are direct to film of the present invention and optics.When used dichroic dye in film or other optical bodies, it is more than another kind that it causes that this material absorbs a kind of polarised light.Be applicable to that dichroic dye of the present invention comprises Congo red (hexichol basic weight a naphthylamine sulfonic acid sodium), methylenum careuleum, luxuriant dyestuff (color refractive index (CI)=620), and 1,1 '-ethyl ester-2,2 '-chlorination cyanine (CI=374 (orange) or CI=518 (blueness)).The character of these dyestuffs and their method of manufacturing are narrated among the Colloid Chemistry (1946) at E.H.Land.These dyestuffs have attractive dichroism and have less dichroism at fiber in polyvinyl alcohol.Observe the Congo red slightly dichroism in PEN.The method that also has other dichroic dye and make them discussion in Kirk Othmer encyclopedia of chemical technology the 8th volume 652-661 page or leaf (1993 the 4th edition), and the reference of being quoted there.

When the dyeing of a kind of dichroism is used for when inventing an optical bodies a few days ago, it comprises a decentralized photo, and this dyestuff is not to be attached to continuous phase to be attached to decentralized photo exactly.But it is possible that dichroic dye is attached to decentralized photo.

Dye some polymer system that combines with dichroism and present the ability of light polarization that make to the degree of having nothing in common with each other.Polyvinyl alcohol and some dichroic dye may be used to make the ability with the light polarization of making.Other polymer is such as quasi-polyethylene terephthalic acid (TPA) salt or polyamides Ammonia; Such as nylon-6, when combining, do not present the strong ability that makes light polarization with a kind of dichroic dye.The combination of polyvinyl alcohol and dichroic dye allegedly has ratio, and for example same dyestuff has higher dichroism ratio in other film that forms polymer system.A higher dichroism ratio is pointed out the higher ability that makes light polarization.

The molecule that it finishes this dyestuff by stretching after dichroic dye is attached to optical bodies is arranged in rows in the optical bodies of making according to the present invention and preferentially chooses.But other method also can reach molecules align and embark on journey.Therefore, in a method, make the dichroic dye crystallization to a series of notches that are elongated by distillation or the crystalline solid that comes from solution, they are to be cut, and are corroded or opposite or be formed on the surface of film or other optical bodies before or after optical bodies is adjusted.So the surface of handling can be plated with a room or multilayer top layer, can be incorporated in the polymer substrate and goes, or be used for a sandwich construction, or be used as an assembly of another optical bodies.Notch can have a space number that is predetermined according to a form that is predetermined or pattern between notch, enable to reach the desired optical property of wanting.

In another embodiment before dichroic dye is incorporated into sandwich construction the surface on sublimation dichroic dye is configured in along the interface of a sandwich construction.In other embodiment that also has, dichroic dye is used to fill out again at least in part the not space in a film.This film be make according to the present invention and have one deck or the space arranged more.

G4. adhesive

Adhesive is to be used for blooming of the present invention and device stackingly to other film, and surface or substrate get on.This adhesive comprises that both optically clean and diffuse adhesives, also has pressure sensitive and the adhesive non-pressure sensitivity simultaneously.The pressure sensitive adhesive is normally sticking and can be gone to the surface by gently finger pressure binding when room temperature, but not the adhesive of pressure sensitive comprises solvent, heat or radioactivation adhesive system.The example of useful in the present invention adhesive comprises that those are based on polyacrylic general synthetic; Polyvinyl ethyl ether; The polyisoprene and the polyisobutene that contain diene rubber such as natural rubber; Polychloroprene; Butyl rubber; Butadiene-acrylonitrile polymer; Thermoplastic elastomer; Block copolymer such as styrene-isoprene and styrene-isoprene-phenylethene block copolymer, ethylene-propylene-diene polymer and styrene-butadiene polymer; Polyalphaolefin; Unformed-polyolefin; Silicone; The copolymer that contains ethene is such as the ethylene-vinyl acetic acid esters.Ethyl acrylate and ethyl-methyl acrylates; Polyurethane; Polyamide; Polyester; Epoxy resin; Polyvinylpyrrolidone and nvp copolymer; And the mixture of top material.

In addition, adhesive can comprise the dose such as tackifier, plasticizer, filler, antioxidant, stabilizing agent, pigment, diffusion particle, coagulating agent and solvent.When laminating adhesive was used for being adhered to blooming of the present invention on another surface, the composition of adhesive and thickness should select to such an extent that the optical property of its unlikely interferometric optical film is advisable.For example, when stacked additional when one wishes to have the optical polarizator of height transmission or speculum, then must to require in polarizer or mirror design in the transparent wavelength zone be that optics is peace and quiet to laminating adhesive.

G5. other additive

Remove the film of pointing out above, outside plating and the additive, optical material of the present invention also can be made up of other material or additive, as known in technology.This material comprises that binding material, plating, inserts, compatible agent, surfactant, antiseptic, blowing agent, reinforcing agent, heat stabilizer, impact slow down agent, plasticizer, viscous conditioning agent and other this material.

H. handle

H1. micropore

In some concrete device, also can be film of the present invention provides one deck or has continuous and a decentralized photo more, therein two alternate interfaces enough weak when film when being conditioned and cause careful management that the mean size of hole can be by technological parameter and draw ratio or the selection by compatible agent.Controlling hole can be with liquid, gas or solid backfill in the product of finishing.Hole can connect together with the minute surface optics of optical stack layer to use and produce the desired optical property that has in the film that in the end obtains.

H2. surface treatment

The processing that the film of making according to the present invention and other optics may stand these material surfaces of various adjustings or its arbitrary part they can be easier to carry out such as plated film, dyeing, metallization or stacked processing subsequently.This can be by using such as PVDC, PMMA, the priming paint of epoxy resin and aziridine or by being coated with prime treatment of physics is handled or such as at the unformed crystalline solid of removing of a heat jar mesexine such as corona, discharge, flame, plasma, flash lamp, sputtering etching, electronics.

I. enduse

Optical bodies of the present invention is useful especially as the planes of color film.The thin M of term reflective color speculum or reflection colour comes colorific multilayer optical interference heap layer about a part of only selecting by reflection in a commonplace wave spectrum of interested electricity.Yet optical bodies also can be made as the effect polarizer of reflection according to the present invention.In these are used, the structural similarity of its optical material in narrated in the above in speculum is used.But with different the making comparisons of refractive index of axle in plane orthogonal, these reflectors generally have a much bigger refractive index difference at the axle in a rhizoplane between alternative materials.This big refractive index difference is generally at least about 0.1, can preferentially select for use greater than about 0.15, and is then more available greater than about 0.2 o'clock.

Reflective polarizer has a refractive index difference along between the axle, and is matched with the refractive index along another root substantially.On the other hand, the mirror coating of reflection, the axle in a low plane is having different substantially replacing aspect the refractive index.The optical axis that is elected to be reference in two rhizoplanes generally is two draw directions, and film presents maximum and refractive index difference minimum between alternately along these chosen axles.But the reflectivity properties of these embodiment is single to be reached from the mistake that relies on big refractive index.Therefore, for example more can be used for improving the degree of reflection.

Reflective polarizer of the present invention has many different application, and is useful on the display floater of liquid crystal.Particularly, reflective polarizer can require high brightness show in as an effective color polarizer use with height colour saturation and high outer transmission of band.In addition, this polarizer can be from PEN or similar material, and it is that good ultraviolet filter and absorbing effectively in the ultraviolet ray on visible spectrum limit is constructed.This reflective polarizer also can be as thin infrared sheet polarizer.It also is useful that this polarizer of the present invention is used as safety device, and it has visible (disclosed) and infrared or ultraviolet (hidden) device both is feasible.

In addition, use and can reflect except a narrow spike, for example about 50nm, the blooming of outer nearly all visible spectrum just can obtain the height colour saturation in transmission.When in reflection, watching and since one very the light of the special wavelength of smallest number do not appear in the spectrum, so that film will present is colourless.But, when in transmission, watching film, relying on backlight helping, eyes just may detect very pure light.The reflection of film range estimation and the contrast of transmission will be the contrasts between colourless (for example, showing chrome yellow or silver color) film and the saturated color of very pure friendship degree that changes with angle is arranged.

I1. demonstration backlight

Adopt colour shifting film of the present invention to make to have the demonstration backlight of a series of optical textures.Generally, this demonstration comprise a light source and be placed in light source and the observer between the part of colour shifting film.In a typical application, the major part of at least one polarised light was passed through film once with paper before entering the observer.

Colour shifting film can be the plane, or can make it other geometry, such as cone, cylinder or spheroid.The face of the opening that multilayer film is can be topped backlight can fully maybe can form around a light source and has one or several geometry by the aperture of light.In these structures any one can be used to produce display, it is divided into several displays that can see color from the various angles of watching of object to light, or produce a kind of display, because offering the observer from the zones of different on its surface, the object that various angles are done forming shape can see many colors in its inside from a visual angle.If display is by backlight a composition, it changes time by a light source and one and by blooming the reflecting material that light is directed to the observer is formed.Then its spectrum is got back to part backlight by blooming and can be repeated to circulate until light till running into film on that angle that it can pass through.Actual device must not be a display, but may be luminaire or light source.The desired light distribution patterns of wanting that this light source has utilized 3M spectrum one angular nature and the wavelength launched in the bulb produces.This repetitive cycling matches with the high reflection ability of colour shifting film, produced one than much bright that color shows with conventional display.Illustrate in the several below examples of some features of listing above.

I2. backlit signs

Film of the present invention can be used for combining with distribution light source or several spot light, just as now in Advertisement label or computer backlight in employed routine backlight the same.One smooth reflectance coating has been dyed color by interference equably, its topped open surface backlight.When the observer can change color during by this label.One choose dyed the surface layer film that opaque or translucent lettering look or that coat pigment colour can be coated to reflection by laser or screen printing technology.Another kind method is, by one the word that reflects of the interference formed with the film (non-top layer film) of different color reflection also can be coated on the lettering of making on the film of top layer, and make lettering present the inverse variation of color from the top layer film, for example the top layer film presents with angle has from green to dark red variation, and lettering then shows the variation from dark red to green on identical angle.Many other color combinations also are possible.

Change color on the film of top layer also can be used to " exhibition show " lettering, the advertisement words and expressions or even in big incidence angle by the invisible material object of film, but when vertical incidence, become highly-visible, vice versa.This " exhibition shows " effect can adopt special color emission light or finish with lettering that has dyed color or the material object under the top layer film of reflection in backlight.

The intensity that shows can be in line with the friendship reflection multilayer film in the inside of cavity backlight and strengthen.Use the same method, whole colour balances of demonstration can be in line with a laminated reflective film that preferentially only reflects some color and a low reflection chamber and control.In the present example because by being in line in the transmission of a certain angle, the brightness meeting of selected color incurs loss.If this does not wish to want, wish that then the colour balance of wanting can influence it by a skim at the bottom of giving a broad band multilayer liner film with the dyestuff of suitable color and absorption.

The reflection Coloured film also can be used for dyeing or the combination of the Coloured film finished pigment, and the one side that the latter is placed on the observer with the control that obtains desirable color such as for example, in lettering, eliminate a color transition and produce the background of a color transition.

Backlit signs needs not be the plane, and Coloured film may be used on a plurality of of label, shows such as an illumination cube or a two-sided advertisement.

I3. non-demonstration backlight

Colour shifting film of the present invention also can be used for producing all non-demonstrations backlight.In these show, from one may be daylight, on every side the internal light source of light or special-purpose light source make at least a polarisation of light before the viewed person of transmitted spectrum sees by the colour shifting film secondary.In most application, this is to adopt colour shifting film combined with surface reflection or polarization to finish.A kind of like this surface can be for instance, by the common mirror type that the metal deposition forms, to throw the metal of light or the film of dielectric surface or multiple layer polymer speculum or polarization.

When colour shifting film of the present invention or beneficial when being used for like the speculum reflection or diffusion ground reflecting surface, the substrate of diffusion ground reflection is preferentially selected for use.A kind of substrate like this cause the color (and subsequently by substrate reflection) of tunicle transmission aim at that plane of incidence penetrates or reflect like the tunicle speculum the different angle of reflection of coloured light in plane of incidence arranged.Thereby make the beholder between color transmission and reflection, to distinguish out.Is particularly advantageous such as paperboard or with the diffusion white surface of irreflexive whitewash surface treated in producing a demonstration that changes color with angle.

In other embodiments, this diffusing surface or its part, they oneself may be coloured.For example, a diffusing surface that contains the printing ink characteristic can gather into folds with a color transition.This film has at least at an optical stack layer be transferred to reverberation on the same area of the absorption of inks of spectrum.So when certain visual angle, will cannot see in the object characteristic that in the end obtains, but when another angle, can clearly see (a similar technology that is complementary with the reflection bandwidth and the absorption band of printing ink of colour shifting film can be used for demonstration backlight).Also have among another embodiment, the printing ink of available diffusion white stamps of colour shifting film itself.Translucent before and after this paper is the implication of transmission substantially that is defined as having the diffusion effect of essence.In other words, can be laminated to a surface white or coloured to color transition, and film itself can be printed on also.

In other embodiment, the substrate that film of the present invention is used to absorb the wavelength of tunicle reflection combines, thereby allows the color that shows uniquely by the reflectance spectrum control of film.A kind of like this effect for example when the coloured mirror coating that reflects other wavelength at some wavelength of visible range transmission in the visual field of the present invention is used for combining with a black substrate, just can have been seen.

I4. window design

Blooming of the present invention and device are applicable to the window design such as skylight or secret window.In these were used, blooming of the present invention can be used for and connect together such as the empty batching of the common glass of plastics or glass or enter as constituent element.The windowpane material of Zhun Beiing in this way.Can be made into polarization characteristic make window design to the first time polarised light be transparent basically, but reflection polarised light for the second time basically, thereby eliminate or reduce dazzling.The physical property of blooming also can be adjusted to as telling about in this article, be the windowpane material in certain district of spectrum (for example, the ultra-violet (UV) band) will reflect one or both polarised lights and all reflect, and (for example, visual field) then all transmissions of one or both polarised lights of transmission in another district.This is a particular importance in glasshouse is used, and can utilize reflection and the special wavelength of transmission to control plant there and grow, and blooms and process that other is biological.

Blooming of the present invention also can be used for providing the decorated dormer of transmission special wavelength light to design this window design and can be used for, for example maybe can be used to make its decorating remarkable especially when giving the room a kind of special color or several color (for example, blue or golden) when utilizing wavelength particular lamp Opital control board.

Blooming of the present invention can go with being attached in the windowpane material as the whole bag of tricks known in technology.Therefore, can all or part of of the outer surface of blooming adhesive glass window material for example be got on an optical adhesive is stacked in one embodiment.In another embodiment blooming of the present invention is clipped in the middle of the panel of two blocks of glass or plastics, and the product that obtains at last is incorporated in the window design.Certainly, as this paper narration can instead add or plate and be added on the blooming (for example, UV absorption, anti-photographic fog or antireflection) so that it is more suitable for specialized application, this is its target place always.

The especially beneficial purposes of Coloured film of the present invention in window design is that they are being full of application in the window of sunlight.In this application, from the daytime to the evening, can watch two-way color.When by day the time, the color of this window mainly is the transmission property domination towards sunlight by film.But, when at night the time, almost can't see transmission by film, this moment film color be decided by film towards the reflection of the light source that illuminates the room light source, consequently the shop look that appears at daytime of film for solar simulated.

I5. light fixture

Colour shifting film of the present invention can be used for various lamp applications, comprises the demonstration backlight backlight and non-that the front was narrated.Depend on the desired application of wanting, in shape can be painted or irised colour shifting film equably, and the selectivity of spectrum can be changed into transmission or reflection in the desired wave-length coverage of wanting.And, the light that can be formed in coloured film polarization is used only reflection or a kind of polarised light of transmission, office work light or polarization demonstration such as polarization combine with increase brightness with recirculation light, or want the ground of coloured speculum or filter to become transmissive or catoptrical two kinds of polarizations to film production in application.

In simple example, colour shifting film of the present invention is used as a filter in light fixture backlight.Typical light fixture comprises one and has reflecting element like light source and that comprise a diffusion in the back or the speculum or to the shell on the inner surface of a few topped optical cavity part.The output of light fixture generally comprises one and covers light source in order to avoid the filter of direct viewing or diffuse component.Depend in the ridden special applications of light fixture that light source may be fluorescent lamp, incandescent lamp, solid-state or electroluminescent light source metal halide lamp or even solar irradiation.This latter is propagated by free space to be transmitted to optical cavity with the photoconduction of lens system, light pipe, maintenance polarization or the method that other is known in technology.Light source can be diffusion or like minute surface, and can comprise be used for combining randomized, the surface of depolarizationization with spot light.The element of light fixture can be arranged maybe and can be placed in the shell by the domination of consideration aesthetics and/or function by various structures.This light fixture is at building light, light of stage, outdoor light, demonstration backlight and label and automobile instrument panel.Colour shifting film of the present invention provides the advantage of the output state of light fixture with the angle variant.

I5 (a) light source relevant with direction

Colour shifting film of the present invention is beneficial especially when being used for directionality light.Be used for the sodium vapor lamp of the application of street or workshop light at large such as efficient lamp, generally have in the spectral emissions of having only a main wavelength.When this source of launching combines with colour shifting film of the present invention, can obtain radiative short transverse control on narrow frequency band.For example, when colour shifting film is used the logical making of the herring bone consistent with the emission peak of lamp, so the emission of this lamp only could passed through film near design angle; In other angle, get back to lamp or lamp housing from the light of source emission.Typical monochromatic and golden pinnacle light source comprises low-pressure sodium lamp, mercury lamp, fluorescent lamp, compact fluorescent lamp and cold-cathode fluorescence lamp.In addition, oppositely no longer to need be the narrow logical type with monochromatic source to film, and it only need be to stop or emission by single wavelength in a special incidence angle.Here it is means also availablely have, for example cut and the wavelength that ends near the reflectance coating of the square wave reflectance spectrum of lamp emission.Some special geometry in can being combined in light source and colour shifting film of the present invention includes, but are not limited to as follows:

(a) cylindrical bulb such as fluorescent tube, is wrapped with the film that the vertical incidence transmission that is the peak emission of bulb designs, and in other words, the light of peak wavelength mainly is that major axis from bulb emits in radiation direction in this geometry.

(b) in the reflectoscope shell arbitrarily the geometry of bulb can to make at the in-plane method of radiating perpendicular to shell aperture be with topped this opening of film of peak radiation emitted place transmission that is selected in bulb.This opening can face down or any direction, and can see light at the angle perpendicular to the in-plane of opening, but is not to leave vertical angle basically.

(c) in other words, come the colour shifting film of the emission of transmission bulb in available one or several incidence angle of leaving vertical angle that is designed in of combination of (b) narration.These incidence angles are by providing a slice or several suitable passband to obtain, and are slightly larger than the lamps emission wavelength with wavelength test when vertical incidence.Like this, the emission of bulb is that blue shift at passband enough makes emission peak become transmission under the angle of delegation with the passband duty.

(d) angle of narration distributes to combine with the geometry of narrating in (a) and will provide a columniform bulb in (c), can have in the radiative direction that is being parallel to the bulb long shaft plane its inside people and control.

(e) a polychrome pinnacle light source, for example having the light source of launching the pinnacle at three different wave lengths can combine with the colour shifting film that only has a passband.Therefore, this film one in given three color pinnacles of an incidence angle transmission and each emission peak is done transmission in different angles just.This film can make with many cohorts, and each group reflects in different wavelength region may, or it can be made with a cohort and their higher harmonic wave.Can control the width of first order bandwidth region, thereby the bandwidth width of harmonic wave is given in the desired transmission band gap of wanting of the harmonious wave reflection interband of the first order.The combination of the pinnacle light source of this film and polychrome will occur from " in vain " color light source division light significantly it being assigned to its each other color.

Because is little with the spectrum mobility of angle near vertical incidence the time, be rare effect so incide colour shifting film than the angle of elevation when angle of light is controlled at vertical incidence.When for example, the bandwidth that relies on the width of the lamp line of departure and passband is vertical near the angle control of minimum may be little to+/-10 degree or big to+/-20 spend or+/-30 spend.Certainly, to the lamp of single line emission, do not have the restriction of angle control, for or the aesthstic or reason of the conservation of energy, it may be desirable less than the free space that can reach lamp that limit angles is distributed as the angle, and it is degree typically+/-90 on one or two level and vertical plane.For example, depend on client's needs, may wish angular region is reduced to+/-45 degree that+/-60 degree or only be+/-75 are spent.

When high angle incident, become 45 degree or 60 degree angles such as normal to colour shifting film, angle control is more efficiently.In other words, when these angles, the energy frequency band is than shift to blueness with higher nm/ degree speed when vertical incidence.Therefore, in these angles, the angle of herring bone emission peak control can remain in the several years, such as+/-5 degree or can be little to+/-2 degree to very narrow passband and the narrow line of departure.

Colour shifting film of the present invention also can be shaped so that the angle output of control lamp in the desired pattern of wanting by the appearance that designs earlier in advance.For example, be placed near the whole or colour shifting film partly of light source and can be shaped as fretful or leg-of-mutton waveform, so that the axle of waveform not the parallel axle that just is perpendicular to fluorescent tube.It is possible that the directionality control of this configuration different angles in orthogonal plane is arranged.

On the angle of emission or detection, work finely though herring bone source and colour shifting film are combined in control light, have only an a limited number of source to have narrow emission spectrum, thereby limited color is available.In other words, can be done so that it plays as the work in herring bone source in order to obtain radiative similar orientation control to broad band source.Can the topped color of broad band source can be used for of selecting and second film with identical transmitted light source in the film of certain herring bone wavelength zone transmission and the source that is conditioned in conjunction with make from the source/luminous energy that color selective membrane combined transmit is come out once passes through this colour shifting film in design corner.This device can be more than a color job, such as with-redgreenblue system.The proper color of emission of selecting of dependence film will be in desirable angle transmission.Wavelength in other angular emission will not lead to coupling with each or arbitrary band, so dark or different colors can appear in light source.Because colour shifting film can be suitable for one of wavelength broad scope transmission, so in fact people can obtain arbitrary color and be controlled at the viewed whole angular direction of arriving of emission light.

The light source relevant with direction is useful in many application.For example, light source of the present invention can be used for the illumination of automobile instrument panel.The driver is seeing instrument at vertical angle like this, thus can see transmitted light, but light can not reflect windshield or be seen by the passenger.Because they are outside the angle with respect to instrument.Similarly, thus available light source body plan lighting label relevant of the present invention or signal label with direction they can under some angle,, but not be that other angle is awared for example perpendicular to signal label or nameplate.In other words, can be designed to light to colour shifting film, and may detect a different color in another angle in a color of an angle transmission.This will be useful, for example, as carwash or provide the inspection post to vehicle command its near and during halt.Can select the combination of colour shifting film and light source make its when a vehicle near the illumination nameplate and when watching with respect to the non-perpendicular angle of nameplate, can only see green so, but that angle in the vehicle park, for example perpendicular to nameplate, the transmitted light of then perceiving will be transformed into redness.As the colour shifting film of safety device and the combination in herring bone source also is useful, and here colour shifting film is used as a stacked making and light source is wrapped with identical film and is used as a simple nuclear inspection device.Other example of the light source relevant with direction of the present invention gives more detailed narration in some following examples.

Example I5-1

Following Example illustrates the purposes like neon tube of film of the present invention at the making polychrome.

Can seal a white fluorescent fluorescent tube with the reflection Coloured film comes structure to make a bright coloury display light.Made several lamps in this manner, the Coloured film that every kind of usefulness one is different, have kind used uniform Coloured film and two kinds with variable Coloured film.With example B1-1, E1-1, E1-2 and the described film production of I6-1 sample.Film is cut into the same with fluorescent tube long, and width is enough to circumference one circle or two circles around fluorescent tube.If once the reflection of Chan Raoing is insufficient, then twining the number of plies can influence colour brightness and the colour saturation that obtains by the total transmittance of controlling topped thing.Variable Coloured film is to use the film identical with routine I6-1 to make, but from tube rather than on the descending blank, the length of downcutting 1.24m (49 inches) across with blank.When the beholder walks out-of-dately, non-homogeneous Coloured film shows flash of light, looks a bit to look like unsettled plasma in a vacuum tube.The purity of color is high enough to " rainbow " apperance to a clear and definite additive effect that has a change color from pipe central authorities to its periphery of fluorescent tube in all bulbs.Even the beholder can walk amount around pipe and watch it from all sides, (for example, the beholder can ad infinitum " catch up with " color of periphery round fluorescent tube but never see the center of this look at fluorescent tube) also can only be the spectrum of watching of vertical incidence at the center.Coloured film can adhere to or stacked with the adhesive loosely.Notice that the air slot of removing between bulb and film with adhesive does not have remarkable influence to the profile of coloured fluorescent tube.

Example I5-2

Following Example illustrates that film of the present invention is in the flexible purposes like neon tube of making.

The fluorescent tubes made of great majority all are that to have only few be circular or U-shaped to straight pipe.The class neon tube of narrating above then can be strengthened the practicality in many application as long as they can be made into arbitrary shape.If but they are substrate with flexible tubular light source, then can further be strengthened.Big core fiber by the 3M exploitation provides a kind of like this light source.This product that is referred to as " 3M optical fiber " can be buied from the 3M company in Minnesota State Paul city on market.Certain percentage point light in optical fiber is by the scattering of TIR angle and the optical fiber of overflowing.This process can be used in the core heart or the outer topped thing and to increase scattering center density and strengthen.Also have, the film of micro-structural can be attached to the limit of fluorescent tube and overflow with the light of guiding fluorescent tube.

Coming topped nominal diameter with the green/dark red film among the example E1-2 all is the sample of peace and quiet and optics micro-structural " fiber " of 1cm.Be coated with a skim with the adhesive that cleans at film and made coloured tape roll of 1 inch wide.This adhesive is a kind ofly to add the synthetic hot-melt adhesive of stabilizing agent by synthetic SIS block copolymer and hydrocarbon tackifier.This adhesive tape is spirally around to optical fiber, and utilization linearly.Because this thickness of 1 inch can not topped entire circumference, so all used thin blank from both sides at latter event.When fiber coiled radius during approximately less than 1/3 meter circle thin blank of the adhesive tape of linear utilization trend towards pursing up and.Even when radius of curvature is 1/6 meter, do not see that spirally the adhesive tape on the fiber corrugates yet.Observed on fluorescent tube with the color of the topped big core fibre of color transition adhesive tape is the same.The lighting that fiber is powered with baby battery.Two kinds or also available each other spiral of more alternative colors come coiling, or with a broadband " silver color " the film Coloured film that alternates, or with (dyestuff or the pigment) Coloured film of routine or plate and alternate.

Can give a series ofly have the object of toroidal to comprise hula hoop and neck band this rainbow profile with little light source.Useful especially light source comprises the fluorescigenic dyestuff in broadband, maybe can put the various combinations of herring bone dyestuff of the polymer core of optical fiber into.

Example I5-3

Following Example illustrates that film of the present invention is the application that flash lamp produces an annex.

Several the colour shifting films of narrating of the present invention are rolled into the tangent plane of cone with circular open or ellipsoidal ends in example B1-1, E1-1, E1-2 and I6-1.The larger-diameter end of each cone is adjusted to the overall diameter of adaptive flash lamp end.Used the size of multiple flash lamp and cone.Larger-diameter cone is about 61 to 91cm (2 to 3 feet), and less, length is in the scope of 152.4 to 609.5mm (6 to 24 inches).Big or multilayer film is when thin (25.4 μ m (1 mil) or littler) when cone, with the PET base-material of 102 μ m (4 mil) cleaning film around getting up, and locate fixedly film on a limit, to increase mechanical integrality with adhesive tape.

Flash lamp and the film of discovery in combination formed an optical cavity that light is assigned to effectively film in all incidence angles.Increase its angle of divergence in each reflection back at the light of divergent beams, even and in the end that does not reach cone reverses direction (angle of divergence is greater than 90 degree) easily behind several secondary reflections towards what the little end of cone was advanced.Therefore, will to continue to propagate back and forth until its tunicle transmission along the length of cone be not that the source is exactly till film absorbs or overflows from the open end on opposite, source to the light that comes out from the source.Annex presents some character that do not reckon with.For example, the center that cone is compared at the cone edge is a kind of different light, and cone can the flip-flop color when the observer waves it at a radian when a people holds cone.

When Coloured film when all incidence angles are made high reflection to a certain color, observed a special interesting effect.Be shown in Figure 38 with this character for the spectrogram of the film of green glow.A cone made from film, and this cone is attached to commonplace light (Maglight) flash lamp with these character, when with respect to awl when when axle 90 is spent, watching, cone is the blue periphery that a redness is arranged.It all is red watching cone when terminal towards two, be yellow then when extreme angles.The green glow effusion of can only less (opening) the terminal hole by cone could changing places.The easiest green glow of seeing when observing cone from the side, this is because the effect weakening of narrating above.Strengthen seeing the light of ease end from childhood.Can append to the reflector of making different shape or be placed into the opening part of close cone tangent plane.

Many other color combination are possible.Also made green/dark red cone, also had the cone that from the blueness to the redness, changes in one after the other higher angle to green.The spectrum of these films is shown in Figure 39 and 18.The bright like that foldable cone of having used a white translucent plastic had been made other object when cone was unlike in all angles when from the illumination of less end.It is in toys store, sell and it be to make the Coloured film that each cross section is used in the type of narrating among the example B1-1 with the maximum cone tangent plane that is attached on the flash lamp and seal by one after the other less.In other words, each tangent plane can be sealed to form a special color coordination, such as for example sequence of a rainbow with different color films.Also can protect blooming to the Coloured film insertion preferably in the inboard of the cone tangent plane of formation in advance.Keep the change color of angle with the combination of this back, preferably select the cone tangent plane of cleaning optically for use.

Example I5-4

Following Example has illustrated the application of film of the present invention in making three-dimensional ornament.

Come topped one to become three-dimensional shaped with the film of example E1-2 (green logical filter), faceted star ornaments are arranged.This star in ornaments shop is made and all facets are flat basically with the plastics of cleaning available from Christmas.Adhesive with a cleaning is attached to Coloured film on each facet.The reflectible color of tunicle is the complementary color of tunicle transmitted colour, and for example 3M is at vertical incidence reflection Red and blue light (dark red), and in the equal angular transmit green, dark red is green complementary color.But, provide the giving young employees remedial-courses in general knowledge and vocational skills luminous effect as film shown in Figure 39.When the incidence angle of about 60 degree, color relation is just in time opposite, this moment green be reflect and dark red be transmission.

What constructed two kinds of forms is the shape ornament, and the both has and cuts into that the little diameter on a limit is the hole of 7/16 inch (11mm), the optical cavity that is become by star to allow light be injected into.In each structure, a little rice the light of Christmas tree of color be inserted in the hole.In second structure, little flash lamp has with one the have an appointment tapered fluorescent tube of broadband mirrors film of 99% reflectivity of visible light is connected with this astrology.(this broadband mirrors film is exactly at United States Patent (USP) the 5th, 882, the type of narration in No. 774).This flash lamp is pancratic type that Maglite company sells.Selected broad light beam, because it can provide the most uniform illumination on all planes on star.Discuss as top energy, the gradient of the elongated circular cone of fluorescent tube can illustrate further to widen this light beam surprisingly from the directive source of part such as flash lamp, no matter can only aware green and peony basically in any visual angle that place on star with the simple geometric figure.In certain very narrow angular region, on plane on the facet, observe blueness.

Can be utilized to produce other attracting life-likely object with any geometry of similar methods.In addition, this object can be rotated.Can inject light or electric power at the point that rotates.Geometry in the example that provides has wide application in the displaying beautiful in colour of a vast scale scope.For example, the advertisement until many meters long or high is showed, may throw light on by the bearing fluorescent tube of one or several hollow.

I5 (b) polarised light annex

Many application requirements polarised lights normally work.This examples of applications comprises optical display, such as LCD (LCDs), be widely used in and analyse a repeatedly laptop computer, handheld calculator, digital watch, fascia shows ex hoc genus anne and the illuminator of polarization and utilize polarised light to increase contrast and the work light that reduces dazzle is used the light of several particularization that coloured polarised light output may be desired, for example all needs dazzle to reduce and the place of coloured " mood " light.Be preferential for the work light annex of raising the efficiency the polarization that has light recirculation in these cases.Near the of a polarised light generally is made up of the shell that comprises light source and a polarizer, and can additionally comprise a reflecting element and/or a diffuse component.Colour shifting film of the present invention can be used as the element of two kinds of polarizations, and especially be used as the polarizing coating (RPF) of reflection or be used as the reflection element, when present and especially as reflex reflector film (RMF), picture is entitled as narration in " the light tool annex that comprises blooming " for the 08/807th, No. 270 at applicant's the U.S. Patent application that awaits the reply jointly.Polarization in conjunction with light recirculation is filled annex will preferentially select a diffused light source for use, it generally comprises light launch site and light reflection, scattering and/or polarizing district.The light launch site can be used as light source and polarizing zone, or this light source can be made up of a smooth launch site and an independent reflector that makes diffusionization.Depend in the special applications of specifying the light annex, diffusing source can be fluorescent lamp, incandescent lamp, solid electroluminescent (EL) light source or metal halid lamp, or with making diffusionization separately, the light source that a polarising surface and a spot light, are far apart or even the combination of sunshine lighting, the latter is by free space propagation, lens system, light pipe.Polarization protects photoconduction or be transmitted to the diffusion polarizer by other method of knowing in technology.

Narrate as the front, colour shifting film of the present invention can be as being placed on the reflective polarizer films (RPF) that light source is handed over, the light-wave transmission of one of them plane of polarization and the light of another plane of polarization then is reflected or can be used as the reflex reflector film (RMF) that is placed on the light source back, face here, two planes of polarization all are reflected from film.In action, the only diffusion ground that is produced by diffusing source is polarized has polarized component (a) and (b) appearance, and this light to go into be to incide on the RPF.This RPF element is suitable on interested wavelength transmission and has the one-level polarized component (light that) light, and reflection in this example, polarized component (a) has orthogonal polarization components (polarized component (b) in this example).In addition, this film with a transmission desired want as the function at visual angle and the light of the wavelength that changes.The result is, the light of the desired color of wanting with polarized component (a) is by the RPF transmission, and the light of polarized component (b) then is reflected back to and is gone in the light annex of diffusionization.Some be originally that the light of being ostracised is changed into the desired polarization of wanting therefrom and by the polarization by reflection element on path subsequently by transmission.This process is continuing, the reflection of its repetition and subsequently be not the desired polarization diffusion of lightization of wanting has increased the desired polarised light of wanting that emits from diffusion polarised light annex number.Consequently one to producing the very effective system of the desired polarised light of wanting.This system is effective in this sense.That is exactly should absorbed light in typical divide in the light polarizer, thus also just can not get having utilized, but be converted to the desired polarization of wanting.The sum of the desired polarised light of launching from annex as a result, of wanting is to have increased.

The lamp annex of here being narrated, light source can be in a series of structure configuration be coupled together as being narrated with polarizer and reflecting element, prospect utilizes color transition reflective polarizer films RPF of the present invention as polarizer and color transition reflex reflector film RMF of the present invention structure configuration as reflecting element, but must understanding, that be exactly looked forward to other material as the RPF of reflecting element and with the various combinations of other material as the RMF of polarizer.For example, in a structure configuration, RPF can be sealed on every side, and it is fully sealed diffusing source.Can use an independent reflector except light source and RPF, this reflector can be the reflectance coating of a diffusion, and it makes polarization (b) light diffusion that reflects from RPF.Can be adjusted at RMF near one side of light source and can be stacked or attached on the light source.In this structure configuration, RPF also can be stacked or be attached, and makes it partly seal the another side of light source.With color transition polarizing coating of the present invention and some application also is possible, and wherein a slice film is rotary with respect to another, and this combination is to be used for lighting accessory it makes polarized light intensity, color and/or degree be controlled by or is transferred to the special requirement at scene.

I6. the application of gardening

Can be produced on the film selected on the spectrum and other optical bodies according to principle of the present invention, they are the application that are suitable for gardening ideally.In greenhouse and agricultural are used, be exactly power and wavelength for the enough light that is suitable for the plant growth to the thing of a main concern of plant growth.Inadequate or unbalanced illumination can cause unbalanced growth of plant or obsolete plant.Too strong light can make soil superthermal and injure plant.Management is a general problem from the heat of sun generation on every side, especially in southern weather.

Color film of selecting on spectrum of the present invention and optical bodies can be used for the application of many gardening, wish energy elimination or the transmission specific light wavelength to the growth of energy Optimal Control plant in these are used.For example, be used for the most effective wavelength of photosynthesis to quicken plant growth and management soil and temperature on every side in order to transmit.Can make the elimination of a slice film optimization ground produce the heat of infrared and visible sunlight wavelength that can not the product effect.

Known that plant plays repercussion to different wavelength in different growths the same period, as shown in Figure 52.In the whole cycle, be inefficient at the wavelength of 500-580nm scope, and wavelength does not have growth response in two scopes of 400-500nm and 580-800nm.Similarly, plant is insensitive to the infrared wavelength of having crossed about 800nm, it has constituted the important component part in the sun emission, can reduce heat widely and can allow the additional light on useful wavelength that plant is grown concentrate so remove these wavelength from solar spectrum.

The business-like lamp that is used for the greenhouse is effective at other the light inspiration degree that quickens photosynthesis and plant.This lamp is replenishing with the unfiltered sunshine of the nature of opposing the most commonly.The energy of lamp emission is at blue (about 400-500nm), redness (about 600-700nm) or far infrared (about 700-800nm) be to be used for tachyauxesis.A kind of common business-like growth lamp 450 and the 660nm place its maximum arranged, beyond 700nm, almost do not have wavelength emission.Another kind of common source has high emission and Hu far infrared wavelength that high emission is arranged in blue and redness.The lamp that is transmitted in the 500-580nm range of wavelength be referred to as " safety lamp " no matter because their emission be in low inspiration zone and be all not influence plant valuably or nocuously to grow very much.

The light source that is used for general illumination often is to be made into finishing and " growth illuminator " similar result.In fact slowed down growth from the wavelength of some sources output, but this point can be matched and compensated by light source with other.For example, use low-pressure sodium lamp can suppress chlorophyllous synthetic separately, but when low-pressure sodium lamp combines with fluorescence or incandescent lamp, produced normal photosynthesis.The common pairing that is used for the commercialization lamp in greenhouse comprises (i) high-pressure mercury lamp and metal halid lamp; (ii) high-pressure mercury lamp and mercury lamp; (iii) low-pressure sodium lamp and fluorescence and incandescent lamp; And (iv) metal halid lamp and incandescent lamp.

In the environment in greenhouse, color selective membrane of the present invention and optical bodies, when be used alone as colour filter or with the reflection pad set fashionable for the growth of optimal plant be useful to concentrating the desired wavelength of wanting.This film and optical bodies can be reinstated with normal unfiltered sunshine one, and perhaps they can make up with artificial wideband light source and control from the source wavelength of light emitted.This light source includes, but are not limited to incandescent lamp, fluorescent lamp such as heat or cold-cathode lamp; Metal halid lamp, mercury vapor light, height and low-pressure sodium lamp, solid-state or electroluminescent lamp, or the sunlamp that is coupled with the pigment selective membrane on the optics of knowing or filter.To do more detailed narration to several filtrations/central system, this may be used for managing the quantity of coming the light that the optimization wavelength transmission for photosynthesis and other plant light inspiration increases in the heat of greenhouse.

Figure 53 to 56 shows the useful design of cold reflector and color selection speculum, and wherein speculum is to be used for that the desired component of wanting of solar radiation is reflexed to indoor handle to emit outdoor to the useless infra-red radiation of plant growth.These figure also illustrated let pass desired radiation of wanting and reflection do not wish the strategy of a transformation of the daylight component wanted.Speculum can be a broadband mirrors, it basically in sunshine language all the wavelength less than about 800nm reflex to indoor, as in Figure 53 and 54, or this speculum can leach infra-red radiation on spectrum and to the grow component of undesirable visible spectrum of plant.Figure 55 and 56 shows structure green glow (from about 500-600nm) and infrared light (from about 800-2000nm) tunicle transmission or reflection in these structures and withdraws from indoorly, and is reflected or directly in the transmission inlet chamber by the dark red light that blue light (from about 400-500nm) and ruddiness (from about 600-800nm) are formed.The film that illustrates has the layer thickness distribution of double-form (for example to produce necessary reflectivity properties, one group in the described film of Figure 56 will reflect green wavelength, and other one group be as U.S. Patent application the 09/006th, the heap floor of No. 118 described 2 or 3 material infrared external reflection/visible transmissions, the name of described patent application is called " multicomponent optical bodies ").At Figure 55, the angle of reflection of a zone of reflections in design in the biobelt reflectance coating then is ruddiness (600-800nm) with another band of reflect blue (400-500nm).Depend on the scope at needed angle, be designed to be the film that moves by the pattern shown in Figure 56 and also can in Figure 55, illustrated pattern move.Provide a kind of like this example and approximate needed angle of film below.Be still in Figure 55, the color selective membrane be stacked or by support on a transparent substrate or open-frame, the wavelength of not wanting so just can pass through.Two kinds of different types of system have been described in Figure 56, this be film can use separately or with broadband reflection device combination, and film is for filtering the direct sunshine that impinges upon on the film, also plays effect for the light from the change direction of broadband reflector reflection.Can make other filter according to the present invention, it provides the wavelength that promotes specific plant part growth.For example, those aim at the wavelength that promotes flower growth rather than stem growth can to make main transmission to the color selective membrane.The selection wavelength of light also can be controlled the motion of plant with making a return journey.Because it is to rotate plant periodically that plant has the common practice of tendency in the plantation plant that turns to light source (phototropism), some business-like product physically rotates this problem that solves around this plant with light source.Can make film according to instruction of the present invention is made into it specially and leaches the wavelength that is used for the plant photoreceptor and feel and shift to light (mainly be blue) and allow other useful wavelength by going.

Though Figure 53 is used as radiation source to 56 account for color selective membranes with sunshine, color selective membrane of the present invention and optical bodies also can directly or in advance be filtered good artificial light sources in order to the spectrum that is provided by these films further to be provided with one or several.In some cases, would rather seal or phase shaft color selective membrane directly with artificial source's coupling, light source mainly is emitted as and controls the plant desired wavelength of wanting of growing so actually.Also can directly be laminated to the roof in the typical greenhouse of composition of cleaning and/or the lath of wall to the color selective membrane, make the most only desired component of wanting in the inlet chamber.Otherwise this lath can be joined together with lath and is extruded to one or several color and selects multilayer heap layer.For the purpose of all light in wanting inlet chamber should be an accurate wave-length coverage, would rather there be film to be loaded on the heliostat or other usefulness moves a mechanical device at the angle of the sunray that compensates all day.Have only weekly or such as only have weekly every month from level or the income that vertically changes angle also can finish with flying colors towards the better simply mechanical device of the lath in south.

The light that one or more reflectors also can be used to guide filtration be to will going to the place, and understood that the physical form of various reflectors and/or color selective membrane can be used for scattering light the indoor desired part of wanting of optical registration or crossing the indoor desired part of wanting.Except the purposes pattern that these had been narrated, this film can be used as indivedual plants the packing of having filtered or with the form of film or with thin blank or the mulch cut as an aquarium illumination that is placed on reflector between plant and soil or is used for water plant as reflector and filter.

Except making of having narrated of front be exclusively used in to plant grow otiose transmission or reflective infrared and/or green glow the film of selecting on the spectrum, a kind of design controlled generally from the ruddiness sum of about 660-680nm and is useful especially from the film of the far-red light sum of about 700-740nm to the growth of controlling plant generally.Pointed out that ruddiness should maintain on 1.1 the level (noting correcting) or a bit high so that reduce elongation and force plant to go out piece or propagation here to the ratio of far-red light, cause denseer, denser plant growth.In addition, by accurately controlling red/red ratio far away and wavelength irradiation subsequently.Many plants can be forced into bloom or remain on growth conditions.The certain plants kind can be controlled in red dosage red or far away few as one minute.Plant to the response of red and far-red light in people such as J.W.Braun " leaf relevant and the distribution of fruit in the raspberry canopy " with the light micro climate, and narrated in TheoJ.Blow " new development that Easter lily is highly controlled ", wherein the former is published on 64 (5) the Journal of HorticulturalScience565-72 (1989), the latter is published in Hort.Re.Instit.of Ontario, VinelaudStaimm is on the Ont.LOR2EO.

The trial of the red red ratio far away of control in the past is to have utilized pump to advance the block liquid of light in the cavity between two blocks of panels of the sandwich wall structure in greenhouse.So because be difficult to add and remove liquid and unsatisfactory.Other trial is at roof assembling Coloured film, if if but the plant variety in the greenhouse often changes or outdoor weather condition has had that to change this be unmanageable.Color selective membrane of the present invention is most desirably to be suitable for this application.Red/red ratio far away can be with changing thickness gradient or controlling to allow the desired wavelength of wanting can arrive plant with the angle that changes film.In order to compensate variation to the needs of the variation of outdoor condition or different plant varieties.Preferably film with or be used or stowable mode device in the greenhouse, for example along roof line with can leaving behind or Volume formula masking piece that Volume gets up, or more than plant high-quality, flatly spur with a masking piece cloth.In other words, can be for independent plant or flora structure film else wrap into thing.

Film of the present invention also can with common speculum together with the intensity that is used for controlling the desired arbitrary part wanted in the solar spectrum that arrives plant.In general, it is desirable will being exposed to plant under the constant wavelength that helps plant growth and the intensity in all day.But a typical sun-drenched date, the peak value of light intensity is about at noon, and this light intensity may surpass concerning many plants; The temperature of leaf usually rises, and this will reduce the strength of plant.Arrive the light intensity of plant in the time of preferably will reducing at noon so that a more uniform level to be provided in all day.For example, when being exposed to 600 μ mol/s-m ²The horizontal rose full blast ground of maximum bloom, and when 11 o'clock of morning of 45 ° of winter months of latitude, often can obtain this intensity.The light intensity that is reduced between 11200 and 1200 can be improved plant products.Common speculum and our being used in combination of wavelength selective membrane, illustrated as Figure 56, can change the light intensity that shines on the plant by different time by day.For example, in the use of Figure 56 visible light speculum, it is during this period of time the highest to refuse can to interrupt sunshine incident from the portions of light that the sun comes by the direction of the angle of reflection of reassigning it.Other combination of its shield or curtain also can be used for controlling light intensity with our wavelength selective membrane.

Example I6-1

The colour shifting film (especially, dark red logical filter) that following example explanation is made according to the present invention, it is particularly suitable for the application on the gardening.

By coextrusion processes, generate to make on the line at a continuous flat film and comprise 417 layers multilayer film approximately.This multilayer polymeric film is made with PET and Ecdel9967.(as United States Patent (USP) the 3rd, 801, No. 429 narrated) produces about 209 layers with the pay-off method by extrudate, and they have approximate linear thickness gradient from one deck to one deck.

With an extruder,, intrinsic viscosity (IV) for the PET of 0.60dl/g is sent to pay-off, and is transmitted Ecdel with the speed of the big self 41kg/h with the speed of about 34.5kg/h.After pay-off,, PET is sent to the both sides of extrudate with the total flow of about 6.8kg/h as edge protection interlayer (PBL) with same PET extruder.Then, material stream by one asymmetrical, have the multiplier design than the two times multiplier (United States Patent (USP) the 5th, 094, No. 778 and the 5th, 094, No. 793) that is 1.50.The ratio of multiplier is defined as, in trunk line, produce average thickness remove the following ducted average thickness.Selecting this multiplier ratio is in order to stay next spectrum gap between two zones of reflections of two groups of 209 layers of generations.Every group 209 layers all have the approximate layer thickness distribution that is produced by pay-off, and overall thickness scale factors is by multiplier and the decision of film extruding rate.ECDEL smelting process equipment maintains about 250 ℃, and PET (optics) smelting process equipment maintains 265 ℃, and pay-off, multiplier, top layer melt-flow and mould maintain about 274 ℃.

In this example, the pay-off that is used for making film is designed to, and provides the thickest and ratio and be 1.3: 1 linear layer thickness distribution under isothermy.In order to obtain less ratio in this example, pay-off is applied a heat distribution.The part of making in the pay-off is heated to 285 ℃, is heated to 265 ℃ and will make the thickest part.In the method, thickness is greater than the thickness with isothermal pay-off operation gained, and the thickest thickness is thinner than the thickness that obtains in isothermal operation.Mid portion is arranged to follow at two linear temperatures between extreme distributes.Total effect is to obtain a narrower layer thickness distribution, and this distributes and produces narrower reflectance spectrum.Some thickness errors are introduced by multiplier, and are the reasons (referring to Figure 57) of the medium and small difference of spectral characteristic of each zone of reflections.Regulate the speed of casting wheel, so that last film thickness is accurately controlled down to last color.

After multiplier, with the speed (total) of about 28kg/h, add the PBL (top layer) of thickness symmetry, this speed is that the 3rd extruder provides, after this, material flows through a film mould, leads on the water-cooled cast wheel.Inlet water temperature on the casting wheel is about 7 ℃.With a high pressure pinning system the extrudate pinning to casting wheel.The thickness of pinning metal wire is approximately 0.17mm, and applies the voltage of about 5.5kV.The operator manually is placed on the pinning metal wire on the point that leaves blank about 3 to 5mm and contact with casting wheel, makes the casting blank have a smooth shape.Order length adjustment instrument (LO) and tentering equipment with routine are regulated the casting blank continuously.Under about 100 ℃, the length adjustment of blank is about 3.3 to extensibility.In stenter, with about 26 seconds film is preheating to about 100 ℃, and along laterally, with the speed of per second about 16% film is stretched to extensibility and is about 3.5.The final thickness of the film that obtains at last is about 0.06mm.

The spectrum of the film that obtains at last (under vertical incidence) is shown in Figure 57.Notice that this spectrum has two delustring frequency bands, its center is approximately 550 and the 800nm place.800 and 550 ratio is 1.45, and it approaches multiplier and designs desired 1.50.Notice that also this film has the approximate complementary color of example E1-2 in all incidence angles.For horticultural applications, need do structural improvement to this film, more such as adding to the red reflex band, to widen its footprint, the near-infrared of spectrum is partly included.Optimization performance in vertical incidence and high angle incident can require to aim at the indivedual films that design in those angle uses.In addition, need with additional plating or form carry out UV protection.

I7. the spectrum bar code in the Secure Application

The personation of file and element and forgery, and the illegal transformation of control material are serious and a ubiquitous problem such as explosive.For example, commercial maintenance personal with aircraft meets suspicious personation part frequently, but lacks a reliable detection method between high quality parts and personation parts, will note when running into patent application specification.Similarly, be actually that the quilt of shaping repacks and claim to be new cassette memory according to the cassette memory of all laser printers of selling as new goods of utmost point Zadoi to 10%.Recognizing and chase after comprehensive all a large amount of article of ammonium nitrate fertilizer that if can be used for explosive also highly induces one.But the expense of existing identification method is very expensive.

There is several method can prove the reliability of article, the integrality of packing or find part, element and raw-material original producton location.Can examine around in these devices certain is several, certain is several to be can examine with independent light instrument etc., and certain is several then to be that the device example of examining that the combination of two aspects is used for file and Packing Intact comprises irised printing ink and pigment dedicated fiber and watermark, commonplace property printing ink and plating, meticulous printing, hologram and the affirmation video retro-reflection paper that can buy from 3M.Only less selection can be applicable to the proof to element be basically because be subjected to the constraint of size, price and durability, the system of suggestion comprises commonplace property film and integrated circuit block.

Miniature label (microtaggant) has been used to search the control material such as explosive.These materials generally are the multiple layer polymers that grinds and be distributed to product.Can decode with light microscope individually in miniature label, to draw about the date of manufacturing and the information of position, the safety diaphragm product had the needs that do not run into for a long time, what it can be examined around being can understand with machine, it be can make but transreplication not, it is flexible and can be used for from approaching microscopical to big all part dimensions of opening, and it can also can readable information be encoded with the machine of special use.

Useful backing in the time of can making equipment safety film or device to color selective membrane of the present invention and optical bodies specially, tag board or stacked excessively can satisfy whole needs.When the oblique angle, color transition characteristic and high reflectance and colour saturation are to be developed two characteristics of authenticating document and packing uniquely, and can design into this film to spectral details equipping unique spectral fingerprint, this can be used for identifying that special a large amount of safety diaphragms use coding to individual other.Can be formed in this safety diaphragm and optical bodies specially the arbitrary desired partial reflection of wanting of spectrum, comprise visible light, infrared light or ultraviolet light.When the evaluation of just wishing to shelter, can be formed in that spectrum shows transparency in the visual field to film but it has the zone of reflections of the transmission that has nothing in common with each other to disclose a spectral fingerprint of sheltering at infrared region.

The example of a coloured safety diaphragm of being described by transmitted spectrum is shown in Figure 58.It show into the design of plane of polarization internal reflection broadband light its blue ribbon edge edge of transmitted spectrum of-900 layers PEN:coPEN polarizer near 400nm.So but can accomplish easily that these goods of 500nm will be bright blue polarizers that changes grey when the oblique angle into.Film among Figure 58 shows a series of very narrow passband, its main close 500 and 620nm, these characteristics are replicated in three spectrum that are overlapped in Figure 58, one side each spectrum take from from film start from 20cm cross blank outside 3cm.Figure 59 illustrates from the spectrum of the 20cm on film limit, but is 2 points for the 4 meters distances of being separated by in following blank direction specifically.This passband has-38% bandwidth at the 500nm place be the 8nm transmission peaks.The slope of this belt edge edge is about every nanometer 5%, have similar slope at the narrower peak at 620nm place, but the 4nm of bandwidth has 27% transmission peak value.These two spectrum almost are the same.The repeatability of the spectrum shown in Figure 58 and 59 represents that this structure has higher repeatability, have control to be better than+/-position of 50% belt edge edge of 2nm or scope approximately+/-0.4%.

The width of constant spectral characteristic is the magnitude at several cm.The length of rolling up from the film of standard film making apparatus is easy to surpass 1 km.Combine with several centimetres width of constant spectral characteristic, the large tracts of land film with unique spectrum " fingerprint " can be used as a label with safety code.This spectrum is because equipment design and comprise the complexity of realization of the process detail of definite resin viscosity and molecular weight, and this spectrum is difficult to such an extent that duplicate.

More complicated spectral fingerprint can be designed into the bar code that removes to provide with the desirable wavelength of the reflection of selectable transmission unique spectrum in the film an interesting areas.

Figure 60 shows the calculating spectrum that by 50 layers of three groups of PET and a refractive index is the film that constitutes of 1.60 coPEN, every group be design wavelength 550nm's or 0.8,1.0 or 1.2 multiple.The optical thickness that one identical beginning is arranged in each group of 50 layers.Above and following curve represented the peak excursion of the spectrum when each has 2%1-σ standard difference.This of film type can 400 in the spectral region of 1000nm 9 to 10 bits of coded data, it is equivalent to other code at 512 and 1024.Extra code can be produced by the intensity that changes each peak; Therefore public by utilizing four different rheobases to exceed 1,000,000 different codes with generation.

Except bag contains 50,20 and 50 layers the intensity at peak is changed rather than 50,50 and 50 layers, Figure 61 shows as outside the spectrum in Figure 60, the details that the fine structure of be worth reappearing is arranged in the spectrum of Figure 60 and 61, and this details can be used for identifying specially a special item.This details can or lean against unordered variation in the product or by make consciously one not or group's varied in thickness obtain.

Figure 62 shows the potentiality that individually continuous product provided the bar code of a spectrum with the film of having compiled sign indicating number.If five track lines show to therefore system that Figure 60 narrated has been modified 25 (coPEN, normally 68nm) and are adjusted to respectively and are 0nm, 6.3nm, 13nm, 26nm and 39nm.Is to be lowered corresponding to less number in the reflection of the peak at 550nm place at that wavelength zone.A product may can make the continuous limit to the pay-off technology with very high potential performance of a product with this method.Also available other several method or combine separately or with the above-mentioned intensity that makes the transmission and the zone of reflections and the method for change in location.

Information is encoded in safety diaphragm of the present invention and the optical bodies goes, for example can individual other be tuned to dark heat, and the refractive power angle coloured silk that can be controlled at visible region produces unique spectrum.This can be thicker than being used for producing those of spectrum among Figure 61, but when infrared when a single heap layer can produce more than a refractive power colour, will need less.

Utilize high or extremely low f-ratio to be worth in other words can making narrow with the less anti-zone of reflections of refractive index difference at the storeroom of making the optical stack layer to produce the reflector of very narrow band.Optical thickness ratio low and high-index material determines the bandwidth at f-ratio value and one-level peak, also controls the luminosity of this refractive power colour.This method for designing can be used to produce narrow more senior harmonic wave, and it can come change face not need the variation of hardware in the rich pay-off by technology controlling and process.

Provide the example of various spectrum bar codes as what how to make that f-ratio value changes from a single pay-off, can make one and have, thereby 2 grades and 3 grades of peaks will be about 650 and the infrared heap layer of 450nm place appearance at 1300nm one-level peak.If another one-level heap layer adds the selection that is depended on f-ratio value in manufacture process in the visual field occurred having nothing in common with each other three peaks of intensity at 550nm.

To f=0.18,0.33 and 0.5 spectrum is shown in Figure 63 to 65 respectively, and a composite diagram in Figure 66.Have 0.18 can seeing of f-ratio value in Figure 63 three peaks are arranged: one at three grades of peaks of 440nm, one 550 one-level peak and one in 640 secondary peak.Has f-ratio value and is 0.33 can from Figure 64, see as three grades of peaks from Figure 22, foretelling and disappearing.One-level peak at 550 places is then stronger.At Figure 65, seen two peaks once more, but in this example,, as expecting, vanish in the secondary peak at 640 places, and are high reflectances at the one-level peak at 550 places at it.As a variation in this scheme, can cut pay-off so that one of them heap layer to have the one-level peak of different f-ratio values and two heap layers all to be placed in than another infrared, in this example, in the variation of the molten stream turnover rate of high index of refraction/low-refraction, on two heaps layer, different optical effects will be arranged with the more senior of them.

The other method that unique spectral information is provided is a control inclination angle spectrum, as the correction by z-axle refractive index mismatch.So reliability may confirm with the spectrum reader that a sample is placed on outside the vertical angle.Also can be sandwich construction and one or more ultraviolets, visible light and/or INFRARED ABSORPTION pigment or in one side or the both sides or the polymer phase combination in the optical stack layer of optical stack layer.In this structure, but the profile of controlling diaphragm makes it reflect at an angle, but since dyestuff to the absorption of light not in another corner reflection.For example, if the film of Figure 63 is detected outside 60 °, the low wavelength zone of reflections will move into the PEN high absorption and this part of the spectrum that can not be detected.Equip a mechanical reader and make the authenticity that test can be used for proving a kind of like this film two different angles.

Of the present invention at the safety diaphragm of selecting on the spectrum with optical bodies also can comprise or in this optical stack layer or be adjacent to the thicker of this optical stack layer, and these also can be used for transmitting the information of the optical check decoding in cross section that can tunicle.This film also can or be imprinted on below the film on-chip figure with color printing, and to combine so that angle according to the observation to be provided may be the mark that maybe can see that covers.Can be with making the optics attenuation obtain colour contrast partly.In this affected zone, compare with unaffected zone a new color just color transition be tangible.Influence the attenuation of a local? preferential method is that the glass of all polymer in film is getted on the temperature and/or carry out mold pressing processing under suitable pressure.The also available high energy particle of the attenuation of local hits in a grand fashion, ultrasonic wave, thermoforming, laser pulse and stretching obtain.As other color selective membrane of the usefulness of having narrated.This safety diaphragm can connect together to improve the contrast of wearability with a hard anti-reflecting surface of plating or an absorption plating.This safety diaphragm also can combine with an adhesive thermal activation or the pressure inspiration and play a label or cross cutting.

Can suitably make safety diaphragm of the present invention or other optical bodies and directly be laminated on file or the packaging material most application by certain size.The spectral signature of these films generally is the very narrow light that reflects minimum.Although the spectral signature of this film generally be limited to infrared in order not have an effect, so the characteristic of this film and color also are used to strengthen the profile of this object with file or packing.

For some application, this safety diaphragm can be used in the discrete material.Method is film to be clayed into power and this powder spread in this material to go.Paint, plating and printing ink can be from utilizing platelet that film of the present invention grinds by formulated.May be under a kind of situation of discrete material of explosive,, preferably avoid adopting directed material this moment if the lax of material will be taken place at an explosion time.Optionally, the multilayer powder can plate to make its energy-absorbing when the explosive incident with an ablator film such as a kind of acrylates.

Safety diaphragm of the present invention and optical bodies can with extraneous proof (for example, exist on the object a coloured reflectance coating may be provable with at non-perpendicular angle the time be that same performance combines) and the combination that proves of instrument read.Can utilize a spectrophotometer to construct a simple mechanical reader.Can buy the spectrophotometer that can satisfy several low price based on ccd detector display of the present invention; Comprise with optical fiber bundle of lines sensing chieftain and hold preferentially selecting for use of being connected with spectrophotometric.Spectrophotometer is with the spectrum sign indicating number that decides film, method be predetermined with costal fold straight at the oblique angle or an angle of the two combination or several angular measurement incide light on the object.

Except the optical property of developing film of the present invention for Secure Application, also can utilize the engineering properties of these films.Therefore, thus for example can be intentionally design film of the present invention to such an extent that make therebetween separating layer have lower resistance anti-ability of intervening is provided.

I8. ornamental application

As what point out, can advantageously be applied to many decorative applications to color transition character of the present invention and get in other place of this paper.Therefore, for example or separately use film of the present invention, or combine with other material, film, substrate, plating or processing and to make wrapping paper, gift paper, gift bag, ribbon, flowers and other object that can do to decorate.In these were used, film may be used as was maybe may be that cutting, pressing mold, the commentaries on classics of wrinkle is subjected to flicker or opposite, and processing is to produce the desired optical effect of wanting or to make the film rolling.

The front only is an illustrative to the present invention's narration, does not want to limit it.So range of application of the present invention should be individually by deciding with reference to additional requirement.

Claims (18)

1. film comprises:

Alternating layer, it is at least by first and second layers of type constitution;

Described ground floor type comprises a strain hardening polymer, and described film is characterised in that:

Described film has a transmission band at least in the visible range, maximum transmission rate is at least about 70%, and when vertical incidence, described transmission band is at 6cm at least ²Surface area on variation less than about 25nm.

2. film as claimed in claim 1 is characterized in that, the polymer of described strain hardening is a kind of polyester.

3. film as claimed in claim 1 is characterized in that, the optical thickness of at least some is between about 0.07 micron and 0.45 micron in the described alternating layer.

4. film as claimed in claim 1 is characterized in that, described film just in time has a transmission band in the visible range.

5. multi-layer polymer film comprises:

A plurality of alternating layers, it has the ground floor type that comprises first kind of polymeric material, and the second layer type that comprises second kind of polymeric material; Described multi-layer polymer film is characterised in that:

Refringence between the two class layers is Δ x, Δ y and Δ z, wherein Δ x is along axle in first, Δ y is along perpendicular to axle in second of axle in first, and Δ z along with mutually orthogonal the 3rd of first and second, and | Δ z | less than about 0.5k, wherein k is | Δ x| and | the greater among the Δ y|.

6. film as claimed in claim 5, it is characterized in that when vertical incidence, described film presents at least 90% first transmission peaks in the visible range, and when incidence angle began from vertical incidence in ± 60 ° scope to change, the change of peak width was less than ± 10cm ^-1

7. film as claimed in claim 5 is characterized in that, when incidence angle began from vertical incidence to change in ± 60 ° scope, transmissivity remained on more than 90%.

8. film as claimed in claim 5, it is characterized in that, when vertical incidence, described film presents in the visible range and has 90%, tangible first and second transmission peaks at least, and when changing when incidence angle begins scope ± 60% from vertical incidence in, the wide variety at described first and second peaks is all less than ± 10cm ^-1

9. optical bodies comprises:

A plurality of layers, they have a repetitive sequence that comprises first and second layers of type at least:

Described ground floor type comprises first kind of polymeric material, and described second layer type comprises second kind of polymeric material; Described optical bodies is characterised in that:

On the visible range, the difference of the refractive index between described first and second layers of type is Δ x and Δ y, and wherein Δ x is along axle in first, and Δ y is along perpendicular to axle in second of axle in first; | Δ x| is greater than about 0.05, and | Δ y| is less than about 0.05; In visible bandwidth λ ± k, the average reflectance of described optical bodies is greater than about 80%, and wherein k is greater than about 10nm; At visible bandwidth (600nm, λ-k-c) and (λ+k+c, in scope 900nm), the average reflectance of described optical bodies is less than about 15%, and c is greater than about 100nm.

10. film comprises:

Alternating layer, it is made of first and second kinds of polymeric materials; Described film is characterised in that:

For the visible light along axle polarization in first, the difference of the refractive index between described first and second kinds of materials is at least about 0.05; For along the visible light perpendicular to axle polarization in second of axle in first, the difference of the refractive index between described first and second kinds of materials is at least about 0.05; For along with the visible light of described first and described second the 3rd mutually orthogonal polarization, the difference of the refractive index between described first and second kinds of materials is less than about 0.05; And described film has one at least about 50% transmission peaks in the visible range.

11., it is characterized in that described transmission peaks is at least about 70% at film as claimed in claim 10.

12., it is characterized in that described transmission peaks is at least about 95% at film as claimed in claim 1.

13. a method that is used to make multilayer polyester film is characterized in that, may further comprise the steps:

A mould surface is provided;

A pinning wire is provided;

Extrude a multi-layer resinous stream between mould surface and pinning wire, multi-layer resinous stream comprises alternating layer, and it is by ground floor type that comprises polyester and second layer type constitution;

Produce enough current potentials at pinning wire two ends, make the layer thickness distortion of at least some layers in the ground floor type; And

The voltage at modulation pinning wire two ends;

Wherein, the modulation of pinning wire voltage is enough to produce one on the film of making of resin flow and is periodic change color basically.

14. a desk lamp tool is characterized in that, comprising:

Tubular light source; With

Coloured level crossing film, it is positioned on the outer surface of described light source, comprises a plurality of alternating layers at least, and described alternating layer is at least by ground floor type that comprises first kind of polymeric material and the second layer type constitution that comprises second kind of polymeric material; The difference of the refractive index between two kinds of layer types is Δ x, Δ y and Δ z, wherein Δ x is along axle in first, Δ y is along perpendicular to axle in second of axle in first, and Δ z along with mutually orthogonal the 3rd of first and second, and | Δ z| is less than about 0.1k, and wherein k is | Δ x| and | the greater among the Δ y|.

15. the light fixture as in the claim 14 is characterized in that, having at least a kind of in described first and second kinds of polymeric materials is negative birefringence.

16. a film comprises:

Alternating layer, it is by ground floor type that comprises first kind of polymeric material and the second layer type constitution that comprises second kind of polymeric material; Described film is characterised in that:

Described first kind of material is negative birefringence; For axle polarization in first, wavelength is the visible light of 621nm, the difference of the refractive index between described first and second kinds of materials is Δ x; For along perpendicular to axle in described first second in the axle polarization, wavelength is the visible light of 621nm, the difference of the refractive index between described first and second kinds of materials is Δ y; For along with described first and described second the 3rd mutually orthogonal polarization, wavelength is the visible light of 621nm, the difference of the refractive index between described first and second kinds of materials is Δ z, wherein | Δ x| and | have one among the Δ y| at least greater than about 0.05; | Δ z| is less than about 0.05; And described film has one at least about 50% transmission peaks in the visible range.

17. film as claimed in claim 16 is characterized in that, described second kind of material also is negative birefringence.

18. a multilayer polymeric film that makes up with diffuse reflection surface is characterized in that, comprising:

A plurality of alternating layers, they are made up of ground floor type that comprises first kind of polymeric material and the second layer type that comprises second kind of polymeric material at least; Described multi-layer polymer film is characterised in that:

At the 672nm place, the difference of the refractive index between two kinds of layer types is for being Δ x, Δ y and Δ z, and wherein Δ x is along axle in first, and Δ y is along perpendicular to axle in second of axle in first, and Δ z along with mutually orthogonal the 3rd of first and second; | Δ z| is less than about 0.1k, and wherein k is | Δ x| and | the greater among the Δ y|; When vertical incidence, described film has a transmission band in the visible range, and its maximum reflectivity is at least about 70%.

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